Energy generation and / or storage device with a reservoir

Abstract

1. A device (2) for generating and / or storing electrical energy, comprising an anode (4), a cathode (6), a separator (8) capable of triggering and / or enabling the generation and / or storage of electrical energy and disposed between the anode (4) and the cathode (6), the separator (8) enabling the transport of at least one compound, and at least one breakable, pierceable, and / or deformable reservoir (10) made of a compound capable of triggering and / or enabling the generation and / or storage of electrical energy, the reservoir (10) having means for bringing the compound and the separator (8) into contact with each other, characterized in that the means for bringing the compound and the separator (8) into contact with each other are, in particular, means for transporting a liquid.

Description

Technical Field

[0001] The present invention relates to an electrical energy generation or storage device that enables user-controlled activation, as well as its manufacture and use. Specifically, the device may enable the activation and / or control of a fuel cell.

Background Art

[0002] (Description of the prior art) Fuel cells function by the transport of ions, typically protons, between two electrodes. For the cell to function, a medium disposed between the anode and the cathode conducts not electrons but, in a simplified version, H + also denoted as, hydronium (H3O +)It must be able to transport ions. This electrolyte within the fuel cell comprises a proton exchange membrane such as a proton exchange membrane fuel cell or a polymer electrolyte membrane fuel cell (PEMFC), and an aqueous liquid that enables the movement of ions. Technological progress has enabled the development of hydrogen-oxygen batteries or enzymatic batteries, particularly environmentally friendly glucose-oxygen enzymatic batteries (see Patent Document 1 by CNRS [French National Center for Scientific Research]). Such batteries are compact, operate at low temperatures (below 80 °C), and in some cases can function with a polymer electrolyte (PEMFC) or an aqueous electrolyte (aqueous solution, biological fluid). Such batteries can be used not only in a fixed mode but also in a portable mode. Therefore, these batteries can be suitable for generating small currents and for household and / or personal use. However, the activation and / or control, and in some cases deactivation, of such devices remain a problem. Conventionally, control has been achieved by opening an electrical circuit. However, any contact between these components of the battery (anode, cathode, membrane) and the liquid can damage these components, especially when these components contain biological materials (plant materials, enzymes, etc.). As a result, the liquid required for the operation of the battery is preferably added to the membrane when the battery first functions. This is generally done by the external addition of liquid to the membrane of the device, particularly by using a pipette as described in Patent Document 2 by Sony, or by using a reservoir as described in Patent Document 3 by Power Knowledge Ltd. Similarly, there are also a number of problems associated with such devices: Firstly, the user must have access to a source of (aqueous) liquid of sufficient purity and quality for the required use and proper operation of the battery. This use must also be able to quantify the volume to be added. This requires the availability of a separate measuring device such as a disposable pipette or dosette, increasing the cost and environmental impact of the device. In addition, this device must be equipped with means for placing the liquid on the membrane. The fact that the membrane can be accessible from the outside suggests, in particular, further contamination problems.Finally, this type of battery can be easily affected by the relative humidity of the environment, making it difficult to store.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, there is a need for an apparatus for generating an electric current that does not have the aforementioned disadvantages.

Means for Solving the Problems

[0005] Therefore, the present invention relates to an apparatus for generating and / or storing electrical energy, particularly electrochemical energy, the apparatus comprising: an anode, a cathode, a separator such as a diffusion layer that enables the transfer of at least one compound capable of triggering and / or enabling the generation and / or storage of electrical energy disposed between the anode and the cathode, at least one breakable, perforable, and / or deformable reservoir made of a compound capable of triggering and / or enabling the generation and / or storage of electrical energy, the reservoir having means for bringing the compound and the separator into contact with each other, and characterized in that the means for bringing the compound and the separator into contact with each other are, in particular, means for transferring a fluid and particularly a liquid.

[0006] A reservoir, such as any reservoir (in English, a "storage tank"), defines a location separate from the energy generation and / or storage location where the contents of the reservoir are used. The reservoir can be adjacent to or even span this location, but does not strictly define the same location. In other words, the reservoir and the electrochemical cell are separate and preferably isolated components. This reservoir can advantageously separate the contents of the reservoir from the anode and cathode, either wholly or in part.

[0007] Accordingly, the reservoir and its contents are involved in the transition of the device from an inactive state to an active state. The deformation of the reservoir and the release of its contents give rise to the ability to activate the device. Thus, the deformation of the reservoir can possibly directly trigger energy generation or storage, or can give rise to an intermediate activated state of the device. In practice, the device can additionally comprise one or more activation means, the configuration of which is selected to either activate or increase or decrease or shut down (or deactivate) energy generation and / or storage. For example, the device can also comprise a switch that can advantageously be operated by the user. Such a switch can comprise, for example, a circuit breaker such as a removable tab. This switch can then be operated by the user either before or after bringing a compound for triggering the generation or storage of electrical energy into contact with a separator. Thus, activation can be direct or can occur in several steps. For example, activation can first occur by pressure on the reservoir (and optionally the release of fluid into the reservoir), and then by the removal of the circuit breaker tab by the user. The subject matter of the present invention also includes the activation of the device by the user, particularly in a continuous manner of several steps or in a single step.

[0008] Advantageously, in the device according to the invention, the anode and / or the cathode comprise an enzyme.

[0009] The reservoir is entirely or partially breakable, pierceable, and / or deformable. For example, the reservoir may comprise parts that can be broken by the user. The reservoir may comprise, for example, a container in the form of a shell (advantageously deformable and / or flexible) having an opening, and retaining means for closing the opening of the shell or container. Thus, this shell, for example a potentially hemispherical dome, forms a cavity for containing the compound and has an opening. The retaining means is advantageously a separating layer or film that seals the opening of the shell or container and forms, together with it, a closed and preferably impermeable receptacle. This type of reservoir is also known by its English name "blister pack" or simply "blister". This reservoir may be characterized in that the surface area of the opening is proportionally large with respect to the total surface area of the reservoir, for example 25 - 45%. However, the present invention is not limited to such characteristics and may be wider or narrower. The retaining means holds the compound inside the reservoir and in particular separates the compound from the anode and cathode at least partially.

[0010] The selection of one or more materials used to make the shell and the separating layer depends on several factors. For example, if the shell is intended to contain a liquid, semi-liquid, gel, or a substance that can move, a layered material with a layer of resistant material is placed in place. It is also possible to select a material that is inert with respect to the material stored in the reservoir [3], or a material that absorbs water vapor, oxygen (or both), to control the atmosphere inside the reservoir and thus preserve the contained product (increase in stability over time) [4]. One or more materials with the lowest environmental impact can also be selected [2]. The materials are generally thermoformable materials [1] and can be selected from the group of materials consisting of: · Polyvinyl chloride (PVC), · Polychlorotrifluoroethylene (PCTFE) (and in particular ACLAR (trademark)), · Cyclic olefin copolymer (COC), · Polyethylene (PE), · Orthophthalaldehyde (OPA), · Aluminum, · Heat-seal lacquer (HSL), · Vinyl acetate copolymer of maleic acid and vinyl chloride (VMCH), · Polyvinylidene chloride (PVDC), · Polyethylene terephthalate (PET), · Glycol-modified polyethylene terephthalate (PETG), · Cyclic olefin copolymer (COC), · Polypropylene, and · Their mixtures.

[0011] The reservoir may also comprise laminates, in particular laminated sheets of these materials. These components have advantageous properties with respect to chemical resistance and / or moisture resistance. For example, PCTFE, PVC coated with PVDC, or polypropylene are particularly well-suited for the reservoir, especially the shell, due to their ability to act as a barrier against air and moisture. In addition, materials combining laminated sheets of aluminum and HSL or aluminum and VMCH are also particularly preferred for producing holding means and / or separating means. Alternatively, materials based on cellulose fibers (such as paper or cardboard) can be considered as advantageous alternatives to these materials from an environmental point of view. In particular, this material can be combined with a film such as a plastic film, and especially with a film of one of the aforementioned thermoformable materials.

[0012] The size of the reservoir can be determined by the amount of the compound (e.g., liquid) to be released. The term liquid encompasses not only compounds or compositions but also semi-liquids (e.g., viscous compounds or compositions), as well as gels.

[0013] The compound for triggering the generation and / or storage of electrical energy housed within the reservoir can be a liquid, solid, or gel, preferably an aqueous liquid, i.e., one mainly based on water or simply ordinary water (which can have different purities: distilled water, pure water, tap water, etc.).

[0014] The compound can be a composition comprising at least one compound capable of triggering the generation and / or storage of electrical energy. This composition includes an electrolyte (a phosphate buffer containing sodium or ammonium sulfate), enzymes (e.g., glucose oxidase and / or FAD dehydrogenase for the anode, and laccase and / or bilirubin oxidase for the cathode), an electron exchange mediator (e.g., ABTS, 1,2-gold-1,4-naphthoquinone, phenanthroline quinone, or pyrene, and one of its derivatives), a cofactor (e.g., NAD + / NADP + , or a flavin coenzyme such as FAD (flavin adenine dinucleotide) or FMN (flavin mononucleotide), a promoter of a substrate (e.g., glucose) (e.g., protoporphyrin IX), and / or an enzyme orientation molecule, i.e., an enzyme or molecule capable of acting on a parasitic or toxic substance (e.g., catalase for decomposing hydrogen peroxide produced by the enzyme glucose oxidase), and can contain or consist of them.

[0015] The means for bringing the compound (e.g., a liquid) and the separator into contact with each other can include the selection of a material that allows for breakage by the user applying sufficient pressure to a part of the reservoir, preferably breakage at a specific point or special region of the reservoir. This is the case for a blister pack for pharmaceutical tablets, where the pressure applied to the shell of the blister pack and its deformation cause the film to close the containment part, but not with a strength sufficient to break and make the tablet available [see 5 - 9]. Since the liquid is not compressible, this arrangement can be suitable for the device according to the invention.

[0016] According to another variant of the invention, the means for bringing the compound and the diffusion layer into contact with each other may comprise piercing means which may comprise at least one part having a potential cut or tip. Thus, these piercing means may be in the form of, for example, needles, blades, protrusions, or spikes. These means are arranged in front of the surface to be pierced, but may also be arranged inside or outside the reservoir. When the reservoir is a blister pack or a shell, the piercing means are advantageously arranged to be actuated by the user pressing on the outer layer of the shell.

[0017] The means for bringing the compound and the diffusion layer into contact with each other preferably comprises a duct towards the separator and / or a protrusion from the separator, the protrusion or the duct being preferably configured to contact a part of the reservoir, and preferably configured to contact directly the holding means when the reservoir is in the form of a blister pack. Thus, the means for bringing the compound into contact with the separator may simply be a mere juxtaposition and / or direct contact of at least a part of the separator with the reservoir, and more specifically, with its breaking region if it exists. Thus, the separator is advantageously configured to comprise a part extending beyond the electrodes (i.e., the anode and the cathode) and positioned in front of the (provided) breaking region of the reservoir.

[0018] The separator can be a diffusion layer or a migration layer. The separator can be a simple space between the anode and the cathode, which is intended to be filled with a compound that can trigger the generation and / or storage of electrical energy. Also, the separator can be integrated on one or both sides of the electrode or can be separate from the electrode. Advantageously, the separator comprises or consists essentially of a material adapted to function as an electrolyte substrate. This material includes woven or non-woven fibers (cotton, nylon, polyester, glass), ceramics, and natural substances (rubber, asbestos, wood). The material can include polymeric materials such as polyethylene, polypropylene, poly(tetrafluoroethylene), and / or polyvinyl chloride, for example perfluoropolymers such as the ionomer Nafion™ made by Dupont. The material can also be a gel such as an ionogel and / or a hydrogel, or an item that enables the formation of a gel.

[0019] However, for home use or use by the general public, the use of porous membranes, particularly those made of cellulose fibers such as sheets of paper and particularly porous papers such as blotting paper or filter paper, is also envisaged. The weight of this paper can advantageously be selected within the range of 10 to 300 g / m -2 and preferably 50 to 150 g / m -2 .

[0020] The thickness of the separator is generally thin but must be adapted to the desired application. Thus, thicknesses of 2 mm to 10 μm, particularly 1 mm to 10 μm, preferably 300 to 150 μm (e.g., 190 μm) can be used. In this way, a paper having a weight of 97 g / m -2 is sandwiched between the two electrodes. The separator can comprise a single or multiple layer / material sheets.

[0021] According to certain embodiments of the present invention, the reservoir of the device may comprise one or more compartments. As will be described below, these compartments may contain the same contents or different contents from each other. However, using this configuration is particularly advantageous for enabling the release of individual doses of a compound or for preparing a composition containing a mixture of components that are unstable over time.

[0022] According to another certain embodiment of the present invention, the device comprises at least one other reservoir, which contains a compound that can trigger the generation and / or storage of electrical energy or another compound that may or may not be able to trigger the generation and / or storage of electrical energy. As will be described later (see below), these reservoirs may contain the same or different contents depending on the desired purpose and may be of the same or different sizes. If the contents are the same, the other reservoir can be used for refilling the device. These reservoirs can be arranged sequentially or positioned on either side of the anode and cathode.

[0023] According to another certain embodiment of the present invention, the device may comprise means for (partial, temporary, and / or final) deactivation of the generation and / or storage of electrical energy. Such means may advantageously be in the form of another reservoir having a structure similar to those described in the present application. Such means comprises means for sucking a compound that can trigger the generation and / or storage of electrical energy and thus enables sucking and storing the compound. The sucking means may be, for example, the presence of a partial vacuum in the reservoir associated with means for opening the reservoir, which enables sucking inside the reservoir. These means may also include a water-absorbing substance for sucking a liquid by capillary action. Other aspects of this particular embodiment will be described below.

[0024] According to certain aspects of the present invention, the device may have more than one reservoir or one compartment, the contents and configuration of which are selected to activate or increase or stop (or deactivate) the generation and / or storage of energy. Such devices are described in detail below. Thus, in one example, the present invention relates to a device comprising means for increasing, decreasing, deactivating, and / or reactivating the generation and / or storage of electrical energy, as described in the present application.

[0025] The anode and cathode of the device according to the present invention are electrodes adapted to be used as a fuel cell. Of course, the device according to the present invention can also comprise a series of anodes and cathodes in a stack. The anode and cathode can be made of metal, for example, having a cathode made of silver and an anode made of nickel plated with chromium. However, it is preferred that the anode and cathode are of a type suitable for biofuel cells and / or enzymatic biofuel cells. These bioelectrodes (anode or cathode) can comprise a substrate made of or having deposited thereon carbon nanotubes, a redox mediator, and an enzyme. These electrodes can be multilayered and advantageously include: · A carbon layer having a high specific surface area for activation, such as a carbon nanotube, carbon black, or a layer of carbon in the form of an aggregate or gel, a carbon-based material having a high specific surface area such as a carbon nanotube or a mesoporous carbon matrix, in particular those obtained from magnesium oxide MgO (see "Templated mesoporous carbon: Synthesis and applications" by Inagaki et al., Carbon 107 (2016) 448 - 473) is preferred, · A mediator layer and / or an orientation layer, and / or · An enzyme layer for catalyzing the oxidation or reduction reaction of the fuel.

[0026] The layer can be disposed continuously on a conductive material that can constitute the substrate of these layers, or can itself be deposited on an inert substrate.

[0027] The conductive material can be vitreous carbon, pyrolytic graphite, in particular "highly oriented pyrolytic graphite" (HOPG), gold, platinum, and / or indium and tin oxide. Preferably, the material consists of vitreous carbon or pyrolytic graphite. As shown in the examples, the bioelectrode can comprise a sheet of carbon nanotubes functionalized with an enzyme and preferably a mediator.

[0028] The nanotube sheet is advantageously applied to the conductive material belonging to a microporous gas diffusion electrode comprising a gas diffusion layer (GDL), which is generally a layer containing carbon fibers. A nanotube sheet suitable for this application is commercially available or can be easily prepared using a suspension of nanotubes in a solvent such as N,N-dimethylformamide (DMF), sonication (e.g., for 30 minutes), and filtration (PTFE filter by Millipore, JHWP, pore size = 0.45 μm, diameter = 46 mm). This method is described in detail in Gross et al. (2017), "A High Power Buckypaper Biofuel Cell: Exploiting 1,10-Phenanthroline-5,6-dione with FAD-Dependent Dehydrogenase for Catalytically-Powerful Glucose Oxidation", ACS Catal. 2017, 7, 4408 - 4416.

[0029] When the fuel of the biofuel cell is glucose, the enzyme that can catalyze the oxidation of glucose at the anode is preferably glucose dehydrogenase (GDH) that catalyzes the reaction. D-Glucose + acceptor → D-Glucono-1,5-lactone + reduced acceptor.

[0030] The receptor or cofactor is generally a flavin coenzyme such as NAD+ / NADP+ or FAD (flavin adenine dinucleotide) or FMN (flavin mononucleotide) bound to GDH. A particularly preferred glucose dehydrogenase is flavin adenine dinucleotide-glucose dehydrogenase (FAD-GDH) (EC 1.1.5.9). The term FAD-GDH encompasses native proteins and derivatives, variants, and / or functional equivalents thereof. In particular, this term encompasses proteins with substantially different structures and / or enzyme activities. Thus, for anodes combined with a cofactor, a GDH enzyme protein having an amino acid sequence having at least 75%, preferably 95%, more preferably 99% identity with one or more GDH sequences registered in a database (e.g., SWISS PROT) can be used. FAD-GDH of Aspergillus species is particularly preferred and effective, but recombinant forms expressed from other FAD-GDHs or Pichia pastoris (rGcGDH) from Glomerella cingulata (GcGDH) can also be used. It is also possible to use an anode using a glucose oxidase (GOx, GOD) type oxidoreductase enzyme (EC 1.1.3.4), which catalyzes the oxidation of glucose in hydrogen peroxide and D-glucono-δ-lactone. This enzyme also binds to cofactors such as FAD (flavin adenine dinucleotide). A particularly preferred glucose oxidase is flavin adenine dinucleotide-glucose oxidase (FAD-GOx). This term encompasses native proteins and derivatives, variants, and / or functional equivalents thereof. In particular, the term FAD-GOx encompasses proteins with substantially different structures and / or enzyme activities. Thus, for the electrodes according to the present invention combined with a cofactor, a GOx enzyme protein having at least 75%, preferably 95%, more preferably 99% identity with one or more GOx sequences registered in a database (e.g., SWISS PROT) can be used. FAD-GOx extracted from Aspergillus niger is particularly preferred.FAD-GDH has higher activity than glucose oxidase and thus has a higher catalytic current. This is highly attractive for the purpose of increasing the power generated in an enzymatic biofuel cell. Note that, contrary to glucose oxidase, the FAD-GDH enzyme does not produce hydrogen peroxide. Hydrogen peroxide, due to its oxidizing properties, may be associated with drawbacks in the stability of the biofuel cell (such as the stability of the membrane, the enzyme within the cathode, etc.).

[0031] In a specific example of a glucose biofuel cell, the reduction of dioxygen occurs at the cathode. The one or more enzymes that can be used may be selected from the group consisting of the mediator ABTS (2,2’-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)), or a laccase enzyme advantageously associated with a mediator such as pyrene, naphthalene, anthracene, or anthraquinone / “orienta”, or a bilirubin oxidase associated with a promoter protoporphyrin IX or the mediator ABTS, (2,2’-azinobis(3-ethylbenzothiazoline-6-sulfonic acid).

[0032] The device according to the invention preferably comprises an item or an electrical circuit connected to an electrical consumer device that enables current to flow. As described above, this circuit may include a switch.

[0033] The device according to the invention is in particular a well suitable for a biofuel cell and / or corresponding electrodes, but the device is not limited to this embodiment in any way.

[0034] Optionally, the device is portable and preferably self - contained. A self - contained device is a device that is housed within itself and preferably does not contain removable parts. Thus, the device preferably comprises a housing or “casing” that can protect the anode and the cathode while allowing the user to access the deformable part of the reservoir.

[0035] According to a preferred embodiment of the present invention, the device is a stand-alone, isolated, and / or device independent of external inputs other than gas. In particular, the device does not require any liquid and / or fuel input.

[0036] The present invention also relates to a method for manufacturing a device according to the present invention. This method includes steps for connecting the elements of the device as described in a functional manner. In particular, this method includes (i) at least one compound capable of triggering the generation or storage of electrical energy between an anode and a cathode, and (ii) the arrangement of a reservoir of liquid capable of triggering the generation or storage of electrical energy, means for opening the reservoir, and means for bringing the liquid into contact with the separator.

[0037] The present invention also relates to a device incorporating a device according to the present invention as a current generator. As a non-limiting example, mention is made of medical tests (for measurement or diagnosis) carried out by an individual on themselves or on a patient at or near a treatment site, i.e., at the time and place of care (also known as "point-of-care testing" or POCT). For example, such tests can be ovulation and / or pregnancy tests. The device can also be for non-medical tests and can include an electronic device or packaging that incorporates a liquid container into its design to activate energy generation.

[0038] The present invention also relates to the use of a device according to the present invention for generating electrical energy, preferably for use in the manufacture of electrical or electronic devices as described in the previous paragraph.

[0039] Another aspect of the present invention is a kit or "parts kit" for making an energy generation device such as an electrochemical cell, for example a battery. Such a kit preferably includes a device according to the present invention accompanied by instructions for use. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The present invention is provided merely as an example and will be better understood through the following description given with reference to the accompanying drawings.

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Mode for Carrying Out the Invention

[0041] Hereinafter, FIG. 1 showing the electrical energy generation device according to the present invention will be schematically referred to. First, different modifications of this device will be described before explaining the mounting form and the energy generation method.

[0042] [Anode and Cathode] The electrical energy generation device 2 includes an anode 4 and a cathode 6. In order to ensure that a redox reaction for generating electrical energy occurs, the anode 4 and the cathode 6 are made of a material that enables ion exchange. The anode and the cathode must have specific properties (thickness, conductivity, surface resistance) selected as functions of the application. These components can be impregnated with enzymes and mediators.

[0043] For example, the anode 4 and the cathode 6 include a sheet of nanotubes, particularly a sheet made of multi-walled carbon nanotubes (MWNT) as described above. In the case of a glucose fuel cell, the sheet of nanotubes is impregnated with mediators and enzymes that enable glucose to be oxidized at the anode and oxygen in the air to be reduced to water at the anode. For example, the anode 4 may include the enzyme glucose oxidase and / or FAD dehydrogenase for the oxidation of glucose, and naphthoquinone and / or phenanthroline quinone as a redox mediator that transfers electrons to the electrode.

[0044] Regarding the cathode, it includes the enzymes laccase, bilirubin oxidase, and ABTS as mediators.

[0045] [Separator] The diffusion layer 8 or the separator is disposed between the anode 4 and the cathode 6. The latter enables the diffusion or transfer of a solution that triggers the generation of electrical energy by means of oxidation-reduction between the anode and the cathode.

[0046] This transfer can be effected by what is called a diffusion layer. The diffusion layer 8 can, for example, be a simple space, or, more preferably, can include or consist of a paper-type material that can diffuse a solution triggering oxidation-reduction by capillary action. It is necessary to find a compromise between its thickness and its tank capacity (void volume).

[0047] This diffusion layer 8 forms a separation layer between the anode and the cathode and can also constitute, at least in part, a diffusion substrate for the electrolyte.

[0048] [Reservoir] The electrical energy generation device of FIG. 1 also preferably comprises at least one reservoir 10 that is deformable. In this variant, the reservoir is associated with means for holding at least one liquid (including a semi-liquid or a gel), which, when released, enables ion exchange between the anode and the cathode and the generation of electricity by immersing the diffusion layer 8. The diffusion layer 8 can be positioned between the anode and the cathode and can have an outwardly extending portion (for example, a tab). All or part of the liquid can be in contact with the fluid by means of a holding means 14 consisting of a separation layer that seals the reservoir 10. The contact with the fluid can be direct or otherwise. The reservoir 10 comprises a shell 12 that forms a cavity in which the liquid is enclosed and a separation layer that seals the opening of the shell 12. This device is also known by its English name "blister pack".

[0049] The shell 12 is preferably deformable. The shell can be made of a material produced by polyvinyl chloride (PVC), a material produced by fluorinated chlorinated resin, cycloolefin polymer (COP), cycloolefin copolymer (COC), polyethylene (PE), oriented polyamide (OPA), aluminum (Al), aluminum combined with heat seal lacquer (HSL), or aluminum combined with vinyl chloride / maleic acid / vinyl acetate copolymer (VMCH).

[0050] The selection of one or more materials used to make the shell 12 can depend on several factors. For example, if the shell is intended to contain a liquid or substance that can move, a barrier layer is placed in place. Also, in order to control the atmosphere inside the ampoule 10 and thus preserve the contained product (increase stability over time), it is also possible to select a material that is inert to the material stored in the reservoir 10, or a material that absorbs water vapor, oxygen (or both). Also, one or more materials with the lowest environmental impact can be selected.

[0051] The liquid held inside the reservoir 10 may be, for example, an aqueous glucose solution that interacts with the aforementioned enzyme to enable the exchange of protons between the cathode 6 and the anode 4. The advantage of this device is that no external input other than oxygen is required to operate the electrical energy generating device 2.

[0052] The liquid remains enclosed within the reservoir 10 until current generation is desired. The isolation of the liquid prevents contamination between the electrical energy generating device 2 and the environment of this device.

[0053] The holding means 14 that seals the opening of the shell 12 holds the liquid within the ampoule. The holding means can be made of one or more of the materials described above. For example, the holding means can consist of a composite film composed of an aluminum layer (optionally coated with a protective layer of polyethylene terephthalate (PET)) and a seal layer (made of, for example, polypropylene or polyethylene). Solutions based on biodegradable materials, such as paper or film made of biodegradable PVC like ECOmply (trademark) sold by Bilcare Research AG, Hochbergerstrasse 60B 4057 Basel, Switzerland, are preferred.

[0054] The holding means 14 can be ruptured under pressure to release the contents of the reservoir 10. Figure 1 illustrates the operating principle of the electrical energy generating device 2.

[0055] In step 1A, the device is in an inactive state. The liquid (or semi-liquid or gel) 28 is confined within the reservoir 10. In step 1B, the liquid 28 is released from the reservoir 10 by the rupture of the holding means 14. Then, the liquid 28 is released. In step 1C, the liquid 28 spreads into the diffusion layer 8. In step 1D, the liquid 28 reaches a portion of the diffusion layer located between the anode 4 and the cathode 6. Thus, the presence of this liquid enables ion exchange between the anode 4 and the cathode 6, which induces the generation of electricity by a redox reaction, and the type of which can vary depending on the selected electrochemical cell.

[0056] [Device for rupturing the separation layer] The holding means 14 can be ruptured under pressure to release the contents of the reservoir 10. To do this, several options can be implemented: · As shown in FIG. 2a, for example, when pressure is applied to the shell 12, it is possible to provide a seal between the shell 12 and the diffusion layer 8 to cause the rupture of the seal 16. In this case, the increase in pressure inside the ampoule ruptures the seal 16. The seal is sized and its material is selected such that the seal ruptures as soon as the pressure reaches a threshold value. It is also possible to provide a weak point in the seal 16 to facilitate this rupture. · Additionally or alternatively, it is possible to provide the holding means 14 with piercing means 18. These piercing means can be in the form of needles or spikes that can be disposed inside or outside the reservoir 10. FIG. 2c shows the piercing means 18 (the number of which can also vary) disposed inside the chamber of the ampoule 10. FIG. 2b shows the case where three piercing means 18 (the number of which can vary) are disposed on the front of the chamber of the ampoule 10 or on the seal outside thereof.

[0057] When the piercing means 18 are used, it is preferable to provide a gap between these means and the holding means 14 to avoid accidental piercing. In this way, the piercing occurs only when a sufficiently strong pressure is applied.

[0058] The external pressure applied to the shell 12 deforms the shell to release the contents of the reservoir 10. This pressure can be applied by the user or by automated hydraulic or pneumatic means.

[0059] [Multi-compartment reservoir] The reservoir 10 of the device according to the present invention may comprise one or more compartments. In practice, it may be advantageous to separate the components in order to trigger the generation of electricity. For example, it is possible to separate the different chemical compounds required for the operation of the cell. However, the combination of the same reservoir over a long period of time can cause undesirable reactions such as degradation. It is also possible to maintain the biomolecules in one or more compartments in a specific state (dry, wet, as a gel, powder, etc.), and the rupture of the various compartments makes it possible to obtain energy-generating compounds (for example, items that are maintained in a dry state and then solubilized by a solvent present in another compartment). The use of multiple compartments not only stores the various components but also provides an optimal reaction. FIG. 3 is a schematic view showing a first variant of a reservoir 110 having two compartments 112 and 113, and FIG. 4 shows a second variant of a reservoir 210 having three compartments 212, 213, and 216. Depending not only on the operation of the electrical energy generation device 2 but also on the type of contents (such as the state of the various compounds) in the reservoir 10, 110, or 210, the various compartments may contain a solvent (such as water), an electrolyte, an enzyme, a mediator, a cofactor, a substrate (such as glucose), or an enzyme orientation molecule. The holding means 14 may be or comprise a seal 16.

[0060] Also, the reservoir may include two separate spaces, each comprising a plurality of compartments.

[0061] [Other elements constituting the electrical energy generation device] The electrical energy generation device 2 may also include the normal elements of an electrochemical cell, and in particular a fuel cell. Thus, the device may comprise a conductive element in contact with the anode (in particular, the side of the anode opposite to the side in contact with the diffusion layer). When the device is supplied with gas, means for diffusing this gas may be arranged to enable the supply of gas.

[0062] Finally, the electrical energy generating device may comprise a substrate, preferably a very rigid substrate, and a trim element such as a strip made of glass fiber, plastic, or polystyrene, preferably a biosource material, surrounding the assembly of the above-described components, except for the reservoir 10 which is accessible so that its contents can be released. The purpose of this element is to fix and protect the device.

[0063] Figure 5 shows a first variant of the device according to the invention in which two reservoirs 10a and 10b are used. Here too, these reservoirs can be of the type described above. Here, reservoir 10a comprises a breakable seal 16 and a liquid 28. Reservoir 10b is located on the other side of the cell and also comprises piercing means located outside the chamber of reservoir 10b for piercing the seal 16. Reservoir 10b does not contain any liquid 28. The diffusion means 8 travels from reservoir 10a to reservoir 10b and contacts both.

[0064] According to this embodiment, it is possible to activate and then deactivate the electrical energy generating device 2.

[0065] Steps 5A to 5C correspond to steps 1A to 1D described above, release the liquid 28 into the diffusion layer 8, and generate electricity according to a reactivatable operation.

[0066] As shown in steps 5D and 5E, it is possible to deactivate the electrical energy generating device 2. In step 5D, pressure is exerted on the reservoir 10b which contains no liquid being discharged. The opening can be achieved by bringing the piercing means 18 into contact with the holding means 14. Then, since the reservoir 10b is in fluid communication with the diffusion layer 8, the liquid 28 can enter the reservoir 10b. As shown in step 5E, means are used to allow the liquid 28 to enter the reservoir 10b at least partially. These means may be, for example, the flow of a gas such as gravity, air (when the reservoir 10b contains a partial vacuum). When a sufficient amount of the liquid 28 has been absorbed or transferred to the reservoir 10b and there is no longer sufficient liquid 28 between the anode 4 and the cathode 6, the electrical energy generating device 2 is deactivated. Of course, it is necessary to predetermine the amount of the liquid 28 in order to enable deactivation.

[0067] The deactivation means comprising the reservoir 10b may be temporary. It is possible to reactivate the electrical energy generating device 2 so as to send the liquid 28 back to the anode 4 and the cathode 6. This can be done by gravity, for example, by repositioning the reservoir 10b or by pressing the ampoule 10b again so as to reinject the liquid 28 towards the anode and the cathode.

[0068] Alternatively, as described above for the reservoir 10b, it is possible for the content of the solution 28 to contain one or more compounds for deactivating the electrical energy generating device 2 as a function thereof. Various deactivation strategies can be implemented. For example, the deactivation strategy can consist of the presence of a compound that absorbs the liquid 28, a change in pH by introducing an acid or a base, a change in temperature, breaking of the secondary / tertiary structure by adding an organic solvent, addition of an enzyme inhibitor that reduces the activity of the enzyme by immobilizing the enzyme, or addition of a salt to stop the hydration of the enzyme. Depending in particular on the nature of the liquid 28 and its amount in the reservoir 10a, other strategies are possible.

[0069] For example, FIG. 6 shows a modified example of a second embodiment of the present invention, which shows an electric energy generation device 2 that can be used multiple times, that is, a multi-use device. According to this embodiment, by arranging a plurality of reservoirs each capable of sequentially discharging the activation liquid 28 of the device, the electric energy generation device 2 can be activated multiple times.

[0070] Here too, these reservoirs can be of the type described above. Here, each of the reservoirs 10a and 10b is provided with seals (16a and 16b) that can be easily broken by pressure. Of course, other means for breaking these holding means, such as spikes as described above, are possible.

[0071] According to this embodiment, steps 6A to 6C correspond to steps 1A to 1D and involve the release of the solution 28A into the diffusion layer 8 and electricity generation by a reactivatable operation.

[0072] In step 6D, due to the evaporation of the liquid or the lack of fuel, the electric energy generation device 2 becomes inactive. The inactivity of the electric energy generation device 2 can be defined as when there is no energy generation at all or when the amount of energy generated is below a predetermined minimum value.

[0073] To reactivate the electric energy generation device 2 (steps 6E and 6F), an action is performed on the reservoir 10b filled with the activation liquid 28B, and this activation liquid can then be discharged by an action (for example, application of pressure) on the reservoir 10b. The operating principle is the same as that described previously.

[0074] FIG. 7 shows a third embodiment of the electric energy generation device 2 that can be reactivated and / or inactivated two or more times.

[0075] In this case, the electrical energy generating device 2 can be activated by exerting a pressure on the reservoir 10A to break the seal 16 (as described above).

[0076] When the electrical energy generating device 2 is no longer in an active state (not activated or not sufficient), the device can be reactivated by injecting the activation liquid again between the anode 4 and the cathode 6, by regenerating the existing solution, or conversely by injecting an inactivating agent. This can be done by the reservoirs 10B and 10C, and the respective contents 29 and 30, as well as their sizes, are determined according to the desired purpose such as the nature of the activation liquid 28 in the ampoule 10A, and increasing or maintaining the activity by the electrical energy generating device 2, or decreasing or stopping the energy generation thereby. Thus, the contents 29 and / or 30 can accommodate refilling of the liquid 28 or other compounds such as biomolecules, electrolytes, mediators, enzymes, or substrates. Also, means for stopping or reducing the electrical activity such as a partial vacuum, absorbents, etc. can be included.

[0077] Figures 8a to 8c are partial schematic views of the arrangement of the reservoirs 10, 10A, 10B, and / or 10C that can be included in the electrical energy generating device 2 according to the invention, as described in the present application.

[0078] The variant shown partially in Figure 8a includes two reservoirs 10 and 10A, each of which can contain the same or different compositions (preferably liquids). The two reservoirs are connected in parallel by a duct 11, which is then connected to, comprises, or consists of a diffusion layer. The two compositions can be released by piercing a separating means (not shown) simultaneously or at different times. In this arrangement, the reservoirs 10 and 10A are separate and different. The compositions contained in the reservoirs can interact with each other only outside their respective reservoirs.

[0079] The variant shown in Fig. 8b comprises a reservoir 10 with two compartments 10A and 10B, each containing the same or different compositions. Compartment 10B can be entirely contained within compartment 10B. Piercing means (not shown) are arranged to enable simultaneous or sequential piercing of compartments 10A and 10B. In particular, the piercing means can allow mixing between the two compositions in compartments 10A and 10B within reservoir 10 before discharging into duct 11.

[0080] The variant shown in Fig. 8c comprises four reservoirs 10, 10A, 10B, and 10C. Its operating principle is the same as that of the variant in Fig. 8a. This figure provides an understanding of how it is possible to affect energy generation by changing the nature of the compositions contained in these reservoirs, i.e., increasing, maintaining, or decreasing them. As in the reservoir shown in Fig. 8a, the compositions can only interact outside their respective ampoules within duct 11.

[0081] [Examples of Embodiments of the Present Invention] An example of an electrical energy generation device 2 has been fabricated. This device is a fuel cell. More specifically, this device is a glucose biofuel cell having the structure shown in Figs. 9 and 10. The electrodes comprise MWNT sheets (see above). These sheets are modified by deposition (pipetting) of a solution of a mediator (10 mmol / L phenanthroline quinone in acetonitrile) in an amount of 80 μL / 0.785 cm at anode 4, and a solution of a promoter (10 mmol / L protoporphyrin IX in water) in an amount of 80 μL / 0.785 cm at cathode 6. After drying the two electrodes, a solution of 5 mg / L FAD-GDH in an amount of 80 μL / 0.785 cm at anode 4, and a solution of 80 μL / 0.785 cm at cathode 6 2 of the amount of a promoter (10 mmol / L protoporphyrin IX in water) are deposited (pipetted). After drying the two electrodes, a solution of 5 mg / L FAD-GDH in an amount of 80 μL / 0.785 cm at anode 4, and a solution of 80 μL / 0.785 cm at cathode 6 2 of the amount of a promoter (10 mmol / L protoporphyrin IX in water) are deposited (pipetted). After drying the two electrodes, a solution of 5 mg / L FAD-GDH in an amount of 80 μL / 0.785 cm at anode 4, and a solution of 80 μL / 0.785 cm at cathode 6 2 of the amount of a promoter (10 mmol / L protoporphyrin IX in water) are deposited (pipetted). After drying the two electrodes, a solution of 5 mg / L FAD-GDH in an amount of 80 μL / 0.785 cm at anode 4, and a solution of 80 μL / 0.785 cm at cathode 6 2The enzyme is added to these sheets by deposition (pipetting) of a solution of 5 mg / L bilirubin oxidase having the amount of .

[0082] As an example, a reservoir 10 made by reusing a drug packaging (plastic blister pack closed by an aluminum foil) was filled with approximately 250 μL of a glucose solution at a concentration of 150 mM in a 0.1 M phosphate buffered saline (PBS) solution. Then, this was covered with a polyethylene film (trade name: PARAFILM M) (a plastic paraffin film on paper manufactured by Bemis North America, Neenah, Wisconsin (USA)). This is a thermoplastic material that is ductile, malleable, does not allow water to pass through, is odorless, cohesive, and translucent (and consequently cannot be used in an autoclave). Then, the reservoir 10 is sealed with an adhesive strip to prevent any unwanted leakage of the glucose solution.

[0083] After drying the electrodes 4 and 6, the electrical energy generation device shown in FIGS. 1 and 2 is assembled as follows: A sheet of absorbent paper, such as Whatman filter paper having a dimension, thickness of 190 μm, and weight of 97 g / m -2 corresponding to the configuration of, for example, a biofuel cell that constitutes the diffusion layer 8 is sandwiched between the two electrodes 4 and 6. This layer of absorbent paper is provided with an extension 5. On the side of the anode 4 that does not contact the diffusion layer 8, a GDL (gas diffusion layer) graphite sheet that constitutes the conductive layer 20 is disposed.

[0084] The conductive and gas diffusion layer 22 made of graphite sheets is also brought into contact with the cathode 6 (on the side opposite to the side in contact with the diffusion layer 8 of the cathode 6). This layer enables oxygen to be conducted to the cathode 6. This layer also constitutes a conductive layer. The diffusion of gas is achieved by concave lines that allow the flow of gas. As can be seen in Figure 9, the gas diffusion layer 22 and the cathode 6 are sized and arranged such that the holding means 14 of the reservoir 10 and the diffusion layer 8 are placed directly in front of each other, enabling the contents of the reservoir 10 to spread into the diffusion layer 8 when the holding means 14 is perforated.

[0085] Finally, the electrical energy generating device 2 preferably comprises a very rigid substrate 24 made of, for example, polyester or paper, and a trim layer 26 made of glass fiber strips (or another material, preferably a bio-source material) surrounding all the above-mentioned components except the following: · The ampoule 10 that is accessible to release its contents, · The opening 27 arranged on the front of the gas diffusion layer 22 that enables oxygen to reach the cell, · The possible opening 31 that provides access to the conductive layer 20 or 22.

[0086] When electrical generation is required, pressure is exerted on the shell 12 of the reservoir 10, and this pressure is sufficient to break the holding means 14 and release the glucose solution onto the expansion part 5 of the blotting paper or the sheet of the diffusion layer 8. The liquid spreads onto the sheet by capillary action, enabling the ion exchange of protons between the cathode and the anode and the resulting generation of current.

[0087] Figure 11 shows the measurement of the energy generated by the above-mentioned electrical energy generating device 2. This measurement is carried out using a potentiostat, where the ends of the counter electrode and the reference electrode are short-circuited together and connected to the anode, while the working electrode is connected to the cathode by a connector such as an alligator clip (not shown). Then, the open circuit potential (OCP) is measured.

[0088] By way of example, the holding means 14 of the reservoir 10 breaks at t = 50 seconds by manual compression of its shell 12, allowing its contents to spread into the diffusion layer 8. After 10 seconds (t = 60 seconds) and 25 seconds (t = 75 seconds), the potentiostat shows voltages of 0.458 V and 0.526 V, respectively. As shown in FIG. 11, the electrical energy generating device 2 continues to generate electricity over time.

[0089] The present invention is not limited to the disclosed embodiments, and other embodiments will be apparent to those skilled in the art.

[0090] In particular, it is possible to fabricate various components of the electrical energy generating device using materials other than those described above.

[0091] The compounds for generating energy can be different from those described above.

Description of the reference numerals

[0092] 2 Electrical energy generating device 4 Anode 5 Extension of the diffusion layer 8 6 Cathode 8 Diffusion layer or separator 10, 110, 210, 10a, 10b, 10c, 10A, 10B, and 10C Reservoir 12 Reservoir shell 14 Holding means 16 Seal 18 Piercing means 20 Conductive layer 22 Gas diffusion layer and conductive layer 24 Substrate 26 Trim layer 27 Opening allowing oxygen entry 28, 29, 30 Liquid contained in the reservoir 31 Opening for accessing the conductive sheets 20 and 22 112, 113, 212, 213, 216 Reservoir compartments

[0093] [References] (1) Lockhart, H.; Paine, F. A. Packaging of Pharmaceuticals and Healthcare Products; Springer US: Boston, MA, 1996. (2) Roggenhofer, A. The Magic Triangle of Blister Packaging. Pharmaceutical Processing. 2013, pp34 - 36. (3) Raina, H.; Jindal, A. Packaging of Non - Injectable Liquid Pharmaceuticals: A Review. J. Appl. Pharm. Sci. 2017, 7(2), 248 - 257. (4) Forcinio, H. Blister Packaging Moves Forward. Pharmaceutical Technology Europe. 2017, pp16 - 19. (5) Kelso, D. M.; Agarwal, A.; Sur, K. US20120107811A1: Burstable Liquid Packaging and Uses Thereof., 2012. (6) Brettschneider, T.; Czurratis, D.; Grimm, A. GB2538846A: Storage Unit, Method for Manufacturing a Storage Unit and Method for Releasing Fluid Stored in a Storage Unit, 2016. (7) Kurowski, D.; Paul, O. WO2012062648A1: Blister Packaging for Liquid and Use Thereof and Method for Supplying Liquid to a Fluidic Assembly, 2012. (8) Kurowski, D.; Paul, O. US20130327672A1: Blister Packaging for Liquid and Use Thereof and Method for Supplying a Liquid to a Fluidic Assembly, 2013. (9) Stange, O.; Hohl, H.-W.; Diederich, R.; Droder, K.; Herrmann, C.; Dietrich, F.; Blumenthal, P.; Stuhm, K.; Bobka, P.; Schmidt, C.; et al. WO2017032674: Blister Packaging, 2015. (10) Wright, D.W.; Aiello, D.; Kroehl, P.; Kayyem, J.F.; Gray, D.S. US9598722B2: Cartridge for Performing Assays in a Closed Sample Preparation and Reaction System, 2017.

Claims

1. An apparatus (2) for generating and / or storing electrical energy, said apparatus comprising an anode (4) and a cathode (6), and a separator (8) disposed between said anode (4) and said cathode (6) and capable of triggering and / or enabling the generation and / or storage of electrical energy, said separator (8) enabling the transfer of at least one compound, and at least one breakable, pierceable, and / or deformable reservoir (10) made of a compound capable of triggering and / or enabling the generation and / or storage of electrical energy, said reservoir (10) having means for bringing said compound and said separator (8) into contact with each other, comprising, wherein said means for bringing said compound and said separator (8) into contact with each other is in particular means for transferring a liquid, characterized apparatus (2).

2. The apparatus (2) according to claim 1, wherein said anode and / or said cathode comprises an enzyme.

3. The apparatus (2) according to claim 1 or 2, wherein said reservoir comprises a shell (12) having an opening and retaining means (14) for closing said opening of said shell (12).

4. The means for bringing said compound and said separator (8) capable of triggering the generation and / or storage of electrical energy into contact with each other comprises piercing means (18) or opening means and optionally comprises at least one component having a cut end or a pointed end, the apparatus (2) according to any one of claims 1 to 3.

5. The apparatus (2) according to any one of claims 1 to 4, wherein said reservoir (10) of said apparatus comprises one or more compartments.

6. The apparatus (2) according to any one of claims 1 to 5, wherein said apparatus comprises at least one other reservoir (29, 30), said at least one other reservoir containing said compound or another compound capable of triggering the generation and / or storage of electrical energy.

7. The apparatus (2) according to any one of claims 1 to 6, wherein said compound capable of triggering the generation and / or storage of electrical energy is a liquid, a solid, or a gel.

8. The apparatus (2) according to claim 7, wherein said liquid is an aqueous liquid.

9. The device (2) according to any one of claims 1 to 8, wherein the means for bringing the compound and the separator (8) into contact with each other comprises a duct (11) and / or an extension (5) of the separator (8), and the extension (5) or the duct (11) is preferably configured to contact a part of the reservoir (10).

10. The device (2) according to any one of claims 1 to 9, further comprising means (10b) for increasing (10b), decreasing (10c), deactivating (10c), and / or reactivating (10b) the generation and / or storage of the electrical energy.

11. The device (2) according to any one of claims 1 to 10, further comprising one or more activation means.

12. The device (2) according to claim 11, wherein the activation means is a switch.

13. The device (2) according to claim 12, wherein the switch comprises a removable tab.

14. Use of the device (2) according to any one of claims 1 to 13 for the generation and / or storage of electrical energy.

15. A disposable device, characterized in that it comprises an electrical energy generation and / or storage device (2) according to any one of claims 1 to 13.

16. The disposable device according to claim 15, wherein the disposable device is a device for medical examination.

17. The disposable device according to claim 16, wherein the medical examination is a pregnancy test.

18. A kit for manufacturing an energy generation and / or storage device, comprising the device (2) according to any one of claims 1 to 13 and an instruction manual.

19. The kit according to claim 18, wherein the energy generation and / or storage device is an electrochemical cell.

20. The kit according to claim 18, wherein the energy generation and / or storage device is a fuel cell.

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