Battery with improved electrolyte and improved electrode

Abstract

The present specification relates to a battery device comprising:-electrodes comprising an anode and a cathode, and-an electrolyte between the electrodes comprising a crystalline material having the composition M2B2O5. X (HOH). Y (NOH), where M and N are alkali metals or hydrogen or mixtures of alkali metals or hydrogen, B is titanium, O and H represent the elements oxygen and hydrogen, respectively, and x and y are 0 to 4 and represent the presence of H +, OH-, N + ions capable of migrating in the crystalline material, in particular at least one of H +, OH-, N + and M + ions is movable to migrate within the crystalline material to at least one electrode, and the at least one electrode is made of a material adapted to chemically interact with at least one of the H +, OH-, N + and M + ions.

Description

Technical Field

[0001] This disclosure relates to the field of batteries, whether in the form of primary cells, fuel cells or rechargeable batteries. Background Technology

[0002] Document WO-2018 / 060656 proposes a particularly promising material for forming electrolytes in supercapacitors. This material is a crystalline solid with an A₂B₂O₅ structure, where A can be an alkali metal and B can be titanium. The properties of this material have led the inventors, who are listed in the document, to consider its application in batteries, as mentioned in the document (specifically on page 12, lines 15-30, see reference to the document). Figure 8 ).

[0003] However, the proposed implementation aims to treat the entire electrolyte in contact with the two electrodes as a “pseudo-battery”, in which the discharge (“rapid on the order of minutes, then relatively slow on the order of hours”) cannot be perfectly controlled, and the shells of the piezoelectric elements PZ1, PZ2, PZ3, etc. still need to mechanically confine or relax the material to block or release the charge.

[0004] Typically, the materials provided for the electrodes are carbon, or metals such as copper, silver, gold, or platinum, used solely for collecting electrons. Summary of the Invention

[0005] This disclosure improves upon the situation.

[0006] To better manage the charging / discharging of the device and increase the energy density that can be stored, a method has been proposed that retains similar materials for the electrolyte but improves the selection of materials for the electrodes by introducing controlled chemical interactions between the electrode materials and ions that can move within the electrolyte materials.

[0007] Therefore, the objective is a battery device comprising: - An electrode, comprising an anode and a cathode, and - An electrolyte between electrodes comprising a crystalline material having the composition M2B2O5.x(HOH).y(NOH), where M and N are alkali metals or hydrogen or mixtures of alkali metals or hydrogen, B is titanium, O and H represent elements oxygen and hydrogen respectively, and x and y are 0 to 4 and represent H that can migrate in the crystalline material. + OH - N + The presence of ions. Device, wherein H + OH - N + and M +At least one ion in the crystalline material is mobile to migrate toward at least one electrode, and said at least one electrode is made of material adapted to interact with the H+. + OH - N + and M + Materials made of at least one of the ions that chemically interact with each other.

[0008] As mentioned above, "chemical interaction" should be understood as the insertion of ions into the electrode, or a chemical reaction between the ions and the electrode material. Therefore, the aforementioned chemical interaction includes one of the following: -The H + OH - N + and M + At least one ion is embedded in at least one of the electrodes, and -The H + OH - N + and M + At least one of the ions reacts chemically (usually electrochemically) with at least one of the materials of the electrode.

[0009] In the device described in the aforementioned document WO-2018 / 060656, migrating ions accumulate near the electrodes, resulting in charge accumulation that allows for the collection, storage, and release of electrical energy, but in a purely electrostatic form. Therefore, the amount of energy stored in a device constructed according to the teachings of document WO-2018 / 060656 is still limited by the electrostatic nature of the stored energy.

[0010] In this paper, the chemical interaction with the electrode allows for more efficient control of charging / discharging and allows for increased energy storage density.

[0011] The existing technology cited above does not envision electrodes being composed of materials that can be used for specific ion insertion or to induce electrochemical reactions with migrating ion substances. Therefore, it does not consider migrating substances in the electrolyte (especially OH-). - H + O 2- It can react chemically with the component materials of the electrode or can be embedded in them.

[0012] Through this embodiment, the battery device of this specification conforms to the microscopic Faraday mechanisms commonly found in the design of rechargeable batteries, primary cells, or fuel cells, allowing for precise control over the charging or discharging of such devices. More specifically, this document improves energy density by adding mechanisms of intercalation, ion absorption, or electrochemical reactions to the electrode surfaces used, and by broadening the selection of migrating substances in the electrolyte. The component materials of the electrodes are then selected to accommodate the migrating substances in the electrolyte to produce rechargeable battery devices, primary cells, or fuel cells.

[0013] Solid electrolytes can be in the form of single crystals, ceramics, pressed powders, membranes, or thin films. Their general formula is M₂Ti₂O₅.x(H₂O) or M₂Ti₂O₅.x(NOH), where M is one or more alkali metals (and / or hydrogen); N is one or more alkali metals (and / or hydrogen); and x can be equal to 0. For simplicity, this electrolyte material is referred to as "MTO" below.

[0014] The electrode material can be in solid, liquid or gas form as described below.

[0015] In a typical implementation, the battery device may include an anode made of a material comprising a metal hydride for reacting with migrating OH groups. - Chemical reactions of ions.

[0016] Alternatively, the anode may be made of a material containing at least one element selected from zinc, iron, and aluminum (or sodium or lithium) for use with migrating OH groups. - Chemical reactions of ions.

[0017] In another alternative, the anode can be made of a material containing dihydrogen ions to react with migrating OH groups. - Chemical reactions of ions.

[0018] As for the cathode, it can contain a mixture of oxygen and water.

[0019] For example, the cathode can be made of a material containing nickel hydroxide (NiOOH).

[0020] Alternatively, the cathode may contain silver oxide (AgO).

[0021] In such an implementation, the cathode can initially be made of a material containing silver (Ag), and then, typically when the cathode is exposed to ambient air (especially a mixture of oxygen and water as described above), silver oxide (AgO) can form at the interface with the electrolyte, as referenced below. Figure 6 Further details of the implementation plan.

[0022] In one specific embodiment, the device can utilize the migration of H in the electrolyte + and OH -Ions, and include: - Cathode, which consists of silver and embedded OH - Made of ionic materials, and - The anode is made of a material with an M2B3O7-type structure, where M is an alkali metal or a mixture of alkali metals, B is titanium, and O is oxygen for embedding H. + ion.

[0023] Alternatively, the device may include: - Cathode, which consists of silver and embedded OH - Made of ionic materials, and - Anode, which consists of graphite and embedded H + It is made of ionic materials.

[0024] In yet another alternative, in a battery device where x=0 and M and / or N comprise at least one element selected from sodium and lithium, the device may include: - The anode, which is made of a material containing elements such as sodium and lithium (e.g., in metallic form), and - Anode, which allows the inclusion of lithium and / or sodium ions.

[0025] For example, such a cathode can be made of materials selected from graphite and M'2B3O7 type structures, where M' is an alkali metal or a mixture of alkali metals, B is titanium, and O is oxygen, for embedding and migrating M. + and / or N + ion.

[0026] In one or more of the above embodiments, the anode material and the electrolyte material can be continuously deposited in the form of thin layers (this embodiment is generally easy to implement when the anode is made of a material having an M2B3O7 structure).

[0027] In one or more of the above embodiments, at least the anode is encapsulated in a resin-based material or equivalent, thereby being sealed to prevent air and moisture.

[0028] In addition, the entire device (anode, electrolyte, and cathode) can be encapsulated in a resin-based material or equivalent, thereby being sealed to prevent air and moisture.

[0029] When the electrode material is in solid form, or when one of the electrodes consists only of ambient air (e.g., the cathode in some of the embodiments described above), a so-called "all-solid-state" battery can be produced.

[0030] More generally, the selection of materials for the anode and cathode can be based on the following: the standard redox potential (E0a) of the anodic couple must be lower than the standard redox potential (E0c) of the cathodic couple. Depending on the choice of electrodes, the implementation scheme can be classified according to the properties of the substances migrating in the electrolyte.

[0031] In using OH - In one embodiment of ion migration, the electrolyte material will generate high-mobility hydroxide ions (OH-) through spontaneous hydration. - ).

[0032] In this case, for example, to manufacture rechargeable batteries, the following options are advantageous: - Metal hydrides (e.g., MgH2) are used as anode materials, and Nickel hydroxide (NiOOH) is used as the cathode material.

[0033] In order to manufacture another type of battery: - Metals such as zinc (or iron or aluminum, or mixtures) can be used at the anode, and A mixture of silver oxide (AgO) or O2-H2O can be used as a cathode material.

[0034] To manufacture fuel cells: -Dihydrogen can be used as an anode material, and A mixture of -O2-H2O can be used as a cathode material.

[0035] In addition, hydroxide ions (OH-) - and hydrogen ions H + The generation of combined migrations is possible and can be used advantageously.

[0036] In fact, by including oxygen vacancies in the structure of the electrolyte material, water vapor can be dissociated into H+. + and OH - Then, these two substances can migrate independently of each other, making the following electrode selection possible.

[0037] For example, silver (Ag) cathodes can typically react with OH- - Ions undergo an electrochemical reaction. At the anode, H+... + Ion intercalation or electrochemical reactions can be achieved through graphite-based compounds, or through electrolyte-like solid materials such as A₂Ti₃O₇ (where A can be an element from sodium (Na), potassium (K), or rubidium (Rb), or through the intercalation of H₂. + Any type of material to ensure.

[0038] The advantage of this implementation is that a first electrode (anode) is grown on a suitable substrate, such as K2Ti3O7, which has the property of intercalating protons, and then a solid electrolyte, such as K2Ti2O5, is grown on the anode given the similarity of crystal phases (e.g., lattice matching), and finally an Ag or graphite layer (which does not cause any deposition or interface problems on the solid electrolyte) is grown to form the cathode.

[0039] This design makes it possible to solve a problem often encountered in the field of all-solid-state batteries: the quality of the electrode / electrolyte interface when two materials have too different crystal structures.

[0040] Other substances present in electrolytes, such as Na, can also be utilized. + The migration.

[0041] By adding sodium to the chemical formula of MTO, we obtain materials such as A2B2O5(NaOH) or A 2-x Na x B2O5, which has highly mobile Na in its structure + ion.

[0042] Therefore, for rechargeable batteries: - The anode material may contain metallic sodium, and - The cathode material may include graphite-based compounds, or A2Ti3O7, wherein A may be [Na, K, Rb] or capable of intercalating Na. + Other types of materials.

[0043] Depending on the migrating ion material, other implementation schemes are of course possible. For example, to utilize lithium ions (Li...) + The migration can be achieved by adding lithium to the chemical formula of the electrolyte material to obtain materials A2B2O5(LiOH) or A 2-x Li x B2O5, each of which has highly mobile Li in its structure + ion.

[0044] Rechargeable batteries can be used in the same way: - Lithium metal as an anode material, and - Graphite-based compounds, or A₂Ti₃O₇, can be used as cathode materials, where A can be [Na, K, Rb] or can be intercalated with Li. + Other types of materials. Attached Figure Description

[0045] Other features, details, and advantages will become apparent from reading the following detailed description and examining the accompanying drawings, in which: Figure 1 [ Figure 1 The image shows the crystal structure of an MTO electrolyte material according to one embodiment.

[0046] Figure 2 [ Figure 2 This shows that water molecules are incorporated into this material.

[0047] Figure 3 [ Figure 3 The figure shows the gain of thermodynamic energy as a function of the percentage of hydration at sites in the material structure, indicating that the more water molecules present, the more stable they are.

[0048] Figure 4 [ Figure 4 The image shows a comparison between the electrode arrangements in the "parallel" configuration (left) and the "lateral" configuration (right) of the material.

[0049] Figure 5 [ Figure 5 The image shows a battery type of a device according to one embodiment, wherein the electrolyte is based on the aforementioned MTO material.

[0050] Figure 6 [ Figure 6 The image shows an embodiment of a device in which the electrodes are based on zinc and silver (which are oxidized at the interface with the electrolyte).

[0051] Figure 7 [ Figure 7 The document shows a prior art device within the meaning of document WO-2018 / 060656, which includes the same electrodes, and in this exemplary embodiment is made of gold.

[0052] Figure 8 [ Figure 8 ] showed Figure 6 and Figure 7 A comparison of the electrical performance of the devices. Detailed Implementation

[0053] The following describes the use of M2Ti2O5 family materials (or "MTO" hereinafter) as solid electrolytes in all-solid-state energy storage devices, where M = [Li, Na, K, Rb, H...] or combinations of these elements (having structures similar to those described in document WO-2018 / 060656, particularly Rb2Ti2O5 and K2Ti2O5). More generally, this paper considers materials with the formula M2Ti... xO 2x+1 The family of compounds (where x is greater than or equal to 2 and M = [Li, Na, K, Rb]) provides this property.

[0054] At the microscopic level, MTO materials are characterized by Ti2O5 2- and Rb2 2+ A layered structure with ionic bonds between planes. This material is layered and can be broken along the planes located between Rb atoms.

[0055] Based on the chemical formula of a compound, non-hydrated or weakly hydrated materials can conduct ionic substances, such as H+. + K + RB + Na + Li + It can combine several cations in its composition, such as (Na,K)2Ti2O5.

[0056] Furthermore, there is the possibility of this being provided by hydrated MTO materials, which are actually highly hygroscopic, particularly in their powder form, and possess the property of spontaneously adsorbing water vapor. De novo simulations using density functional theory have shown that this molecular water preferentially organizes into channels along the crystallographic direction corresponding to the b-axis. Figure 1 and 2 As shown, water is incorporated into the structure through hydrogen bonds with the top oxygen atom of the perovskite structure, corresponding to the most probable configuration according to simulations.

[0057] Therefore, adding water molecules in this configuration represents an energy change of -0.5 eV (PBEsol method) or -0.25 eV (HSE method) at T=0.

[0058] Figure 1 This illustrates the insertion of water molecules, in the presence of Rb atoms (one atom is shown in the diagram). Figure 1 (top right of the oxygen atom O (one atom is shown)) Figure 1 (at the center), hydrogen atoms H (two of which are shown in the center) Figure 1 (to the right of the central oxygen atom) and titanium atom Ti (in Figure 1 The material (located in the lower right corner) forms very strong hydrogen bonds within its molecular structure. This structure, with the general formula MTO, is more specifically referred to here as "RTO" because the M atom in the general formula MTO is an Rb atom. Therefore, Figure 1 This demonstrates that water molecules bind to the RTO (or more generally, MTO) structure, forming two very short hydrogen bonds with the apical oxygen atom of the structure. Furthermore, simulations show that the energy gained by adding water molecules to the structure increases with the number of water molecules in the same chain, as discussed later. Figure 2 and 3As explained in the paper, this is beneficial for the generation of water molecule chains, which in particular can lead to Grotthus-type proton conduction mechanisms in water.

[0059] More generally, the entity that migrates within the water can be one of the following substances: OH - and / or M + Where M = [H, Li, Na, K, Rb] and / or O 2- .

[0060] MTO's hydrophilicity facilitates water absorption.

[0061] like Figure 2 As shown, for MTO materials with M=Rb, water molecules are arranged in the MO plane (O1 represents the apical oxygen of the structure). The molecules themselves are organized into chains (forming channels) in the ab plane, preferably with the ab plane parallel to the deposition substrate (so-called "parallel" reverse direction), or with the ac plane parallel to the substrate plane (so-called "lateral" direction), as shown respectively. Figure 4 The left and right sides are shown, where the lines represent the ab plane of the layered compound.

[0062] Characteristically, Figure 3 The thermodynamic energy gain at temperature T=0 is shown as a function of the hydration percentage at sites in the structure.

[0063] The aforementioned MTO material can then be used as a solid electrolyte (and therefore an ionic conductor), for example in micron or nanometer, planar and crystalline structures, wherein the electrolyte consists of a thin layer of MTO deposited on a substrate S, such as an integrated circuit, using deposition techniques such as PVD (physical vapor deposition) or CVD (chemical vapor deposition), said deposition techniques including, for example, sputtering, pulsed laser deposition, atomic layer deposition, molecular beam epitaxy, reactive plasma deposition or others. The MTO layer is preferably a single crystal and / or microcrystal in the region.

[0064] Alternatively, the electrolyte can consist of a thin layer of MTO obtained by peeling a sheet from a millimeter-scale crystal. This sheet, with a thickness of nanometers (up to several hundred nm), can then be transferred onto an integrated circuit, where it naturally adopts a parallel orientation.

[0065] refer to Figure 5 In both cases, electrodes A and B are deposited in a parallel direction (using vacuum deposition) on each side of the MTO thin layer, or in a transverse direction above and below the layer, such that ion conduction preferentially occurs in the ab crystal plane. Figure 5 (Double arrow in the middle)

[0066] The controlled hydration step for the thin layer can be performed before or after electrode deposition and, if possible, before the encapsulation step. Finally, an encapsulating agent E (such as silicone, epoxy, or conformal coating, polyurethane compound, or others) can be deposited on the whole to “freeze” the selected hydration level.

[0067] Alternatively, the electrolyte can consist of a host and crystalline form of MTO, and thus can consist of single crystals (stacked perpendicular to the ab crystal plane) arranged in one or more orientations, aggregated together in a polymer matrix (epoxy, siloxane, or polyurethane compound). The controlled hydration step of the crystals can be performed before encapsulation in the matrix.

[0068] Two electrodes, A and B, are deposited on either side of the encapsulated single crystal, causing ion conduction to occur in the crystal plane ab, as shown below. Figure 5 As indicated by the double arrows.

[0069] Alternatively, the main device can be produced by casting MTO in an encapsulating agent, followed by the MTO material taking a crystalline form in a membrane, ceramic, or other material. For example, the electrolyte can consist of MTO crystals mixed with at least one organic or aqueous solvent (e.g., 2-methylpyrrolidone, water, ethanol, or others). Fluorinated compounds (e.g., polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), or others) dispersed in the solvent can also be added to improve the device's mechanical stability. The size of the MTO crystals can vary from a few millimeters to hundreds of nanometers. Depending on the solvent chosen, the volume percentage of MTO can range from 60% to 98%. A controlled hydration step can be considered before mixing the powder with the solvent used. Depending on the solvent chosen for device fabrication, the mixing process can be extended to tens of hours and include annealing steps at temperatures up to 150°C. Depending on the intended application, the mixture can then be deposited on a non-sticky substrate (such as a TefloN film) or an electron collection electrode, which can typically interact with ions such as zinc, gold, silicon, sodium and / or lithium (which are metals), or silver oxide (AgO), or others, as detailed below.

[0070] For this purpose, deposition methods may include, for example, inkjet printing, spin coating, or blade coating. The drying step can then be carried out for tens of hours at temperatures up to 150°C. After solvent evaporation, a film with a thickness of several micrometers to several millimeters is obtained. Subsequently, if the film has already been deposited on one electrode, another electrode can be deposited on top of the film. If the film has already been deposited on a non-adhesive substrate, two electrodes are deposited, one on either side of the film. The film and its electrodes can then be encapsulated, providing good mechanical strength and a seal against air and moisture.

[0071] In one embodiment, the electrolyte consists of MTO ceramic pressed at 10 tons for 2 hours at 150°C and sintered at 800°C for 10 hours. Alternatively, 2-5% by mass of PTFE (polytetrafluoroethylene) can be added to the MTO powder to make the ceramic more robust without a sintering step. A polymer-solvent-material mixture (8% PVDF: polyvinylidene fluoride - 84% solvent: 1-methyl-2-pyrrolidone - 8% material) is then used and dried at 25-80°C for several hours. Alternatively, the component powders for electrodes A and B can be placed in a pressing system to fabricate the electrodes simultaneously with the ceramic.

[0072] The possible electrodes for the aforementioned energy storage device must be selected based on the migrating substances in the electrolyte and the type of device chosen. In the considered configuration, MTO material is used as the electrode placed in an electrolyte with a standard redox potential E0. a The anode is made of a material and has a standard redox potential E0. c The solid electrolyte between the cathodes is composed of materials, wherein E0 a <E0 c .

[0073] The following provides various examples of manufacturing anodes and cathodes. By encapsulating one electrode and “exposing” the other to air, an asymmetry can be created between the cathode and anode, which creates the possibility of supplying oxygen or water vapor from only one side of the device and results in a supercapacitor effect.

[0074] OH - Ion conduction can be used in the construction of (non-rechargeable) metal-air batteries. Materials that can be used as the anode include, for example, zinc (Zn), iron (Fe), aluminum (Al), or metal alloys consisting of at least two of the above materials.

[0075] An example of a redox reaction occurring at the anode is: Zn + 2 OH - ⇌ ZnO + H2O + 2 e - Materials that can be used as cathodes include, for example: Silver oxide: AgO, or A mixture of N2 / O2 / H2O gases: Ambient air (with a humidity level greater than 5% and less than 95%, an oxygen (O2) level greater than 15% and less than 25%, and a nitrogen (N2) level greater than 75% and less than 85%) can typically be used. Some examples of redox reactions occurring at the cathode include: O2 + 2 H2O + 4 e- - ⇌ 4 OH - O2 + 2 H2O + 4 e- - ⇌ 4 OH - Other implementation schemes can utilize NiMH (nickel-metal hydride) battery structures. Materials that can be used as the anode include, for example: -AB_5 type alloys, such as those based on rare earth elements (La, Ce, Nd, Pr), such as LaNi5 and its derivatives, or alloys containing elements from Ni, Co, Mn, Al, Mg, Zr, C, Co, Fe, Ti.

[0076] An example of a redox reaction occurring at the anode could be: OH - + MH ⇌ H2O + M + e - M is a metallic element that originally existed as a metal hydride MH (such as TiH2 or MgH2).

[0077] Materials that can be used as cathodes include, for example: - Nickel hydroxide (NiOOH), or -A mixture of metal oxides (Ni-Co-Mg), or -Ni-Co-Al alloy.

[0078] An example of a redox reaction occurring at the cathode could be: NiO(OH) + H2O + e - ⇌ Ni(OH)2+ OH - To utilize proton conduction, materials that can be used as the anode (cathode) can include, for example: -WO3, MoO3, TiO2, H2Ti3O7, H2Ti6O 13 H2Ti 12 O 25 and its substituted derivatives.

[0079] Materials that can be used as cathodes (positive electrodes) include, for example: -Metal oxides: RuO2, MnO2, V2O5, PbO2 -Protonated metal oxides: HCoO2 - Prussian blue analogue materials (“PBA”), such as A x M[Fe(CN)6] y .zH2O - or organic materials, such as PEDOT or HATN.

[0080] In order to utilize Li +Materials that can be used as anodes (cathodes) for ion conduction include, for example: - Graphite carbon derivatives: carbon nanotubes, graphene, mesoporous carbon, etc.

[0081] - Lithium metal (Li).

[0082] Materials that can be used to form the cathode (positive electrode) can be, for example: - Lithium-ionized metal oxides, such as LiCoO2 - Lithium intercalation compounds (e.g., mixtures of metal oxides (Ni-Co-Mg), Ni-Co-Al alloys, PBA Prussian blue structural materials, etc.).

[0083] In order to utilize Na + Materials that facilitate ion conduction and can be used to form the anode (cathode) include, for example: - Carbon derivatives (graphite, carbon nanotubes, graphene, mesoporous carbon, etc.). - Sodium metal (Na) - Sodium alloys: Sodium-tin (Na-Sn), Sodium-lead (Na-Pb), Sodium-bismuth (Na-Bi). -Sodium and alloys with intercalated transition metals: Na-Mn-O, Na-Cr-S, Na-Ti-S, - Tin-based compounds: SnO2, SnSb, -In the electrolyte material family, Na2Ti3O7, Na4Ti5O 12 Layered titanium oxides in the form of NaTi2(PO4)3 can be deposited as solid thin films. -Oxides of vanadium or sodium: NaV₂O₅ Materials that can be used for the cathode (positive electrode) are, for example: - Structural materials such as Prussian blue (PBA). -TiSe2 - Sodium ferric phosphate or sodium nickel phosphate: NaFePO4, NaNiPO4 - Sodium manganese oxide: NaMnO2 - Sodium nickel manganese oxide: Na(NiMn)O2 - Sodium cobalt oxide or sodium chromium oxide: NaCoO2, NaCrO2 Sodium-nickel-cobalt oxide: Na(NiCo)O2 - Sodium copper oxide: NaCuO2.

[0084] Comparative Examples Figure 6 An example of a device according to this specification is shown, wherein: - The electrolyte contains MTO material obtained by implementing the above method, starting from a single crystal or dense polycrystalline material in a solvent, and then dried between two electrodes. The anode is made of a zinc (Zn)-containing material and is encapsulated in resin E to prevent oxidation. - The cathode was initially made of a material containing silver (Ag), but it was not encapsulated, allowing the silver to spontaneously oxidize in the open air and come into contact with the MTO, so that the cathode material was actually silver oxide (AgO), and the remainder of the initial Ag material was used to efficiently conduct the charge to the cathode line Fc (e.g., made of silver, similar to the anode line Fa).

[0085] Manufacturing a device based on existing technology under strictly identical conditions ( Figure 7 ),in: - The electrolyte contains MTO material obtained under the same conditions (starting as a single crystal or dense polycrystalline material in a solvent and then drying it between two electrodes). The anode and cathode are made of the same material, containing gold (an excellent conductor but a blocker of ions). The anode is encapsulated in resin E so that it is in contact with... Figure 6 Under the same experimental conditions as the apparatus, the anode and cathode wires were made of silver, as described above.

[0086] Therefore, according to Figure 6 The implementation scheme utilizes OH- anolyte reacting with Zn anodes according to the following type of equation. - Ion migration: Zn + 2 OH - ⇌ ZnO + H2O + 2 e - At the AgO cathode, since the ambient air naturally contains water vapor (H2O) and oxygen (O2), the chemical equation is of the following type: O2 + 2 H2O + 4 e- - ⇌ 4 OH - AgO + H2O + 2 e - ⇌ Ag + 2 OH - Figure 8 A comparison of the results is shown, and it is also shown that... Figure 6 and 7 Cyclic volt-ampere curves of the device.

[0087] Compared with existing technology devices ( Figure 7 )compared to, Figure 6 The device in the study showed significant improvements. Figure 8In the figure, the redox peaks (dashed curve) indicate the presence of electrochemical reactions controlling the charging and discharging of the device. The capacitance is increased tenfold, and the energy density is increased twentyfold. Furthermore, the reversibility observed during the device's discharge / charge makes it an ideal candidate for manufacturing rechargeable batteries.

[0088] The performance of devices as described herein can be further enhanced by using very thin, stackable layers of electrodes and electrolytes, allowing for greater densification and improved device-to-unit-area performance.

Claims

1. A battery device comprising: - Electrodes, including an anode and a cathode, and - An electrolyte between electrodes comprising a crystalline material having the composition M2B2O5.x(HOH).y(NOH), where M and N are alkali metals or hydrogen or mixtures of alkali metals or hydrogen, B is titanium, O and H represent elements oxygen and hydrogen respectively, and x and y are 0 to 4 and represent H that can migrate in the crystalline material. + OH - N + The presence of ions. Device, wherein H + OH - N + and M + At least one ion in the crystalline material is mobile to migrate toward at least one electrode within the crystalline material, and said at least one electrode is made of material adapted to interact with the H+. + OH - N + and M + Materials made of at least one of the ions that chemically interact with each other.

2. The apparatus of claim 1, comprising an anode made of a material containing a metal hydride for reacting with migrating OH... - Chemical reactions of ions.

3. The apparatus of claim 1, comprising an anode made of a material containing at least one element selected from zinc, iron, and aluminum, for reacting with migrating OH... - Chemical reactions of ions.

4. The apparatus of claim 1, comprising an anode made of a material containing dihydrogen for reacting with migrating OH groups. - Chemical reactions of ions.

5. The apparatus according to any one of the preceding claims, wherein the cathode comprises a mixture of oxygen and water.

6. The apparatus according to any one of the preceding claims, wherein the cathode is made of a material comprising nickel hydroxide (NiOOH).

7. The apparatus according to any one of claims 1-5, wherein the cathode comprises silver oxide (AgO).

8. The apparatus of claim 7, wherein the cathode is made of a material comprising silver (Ag), and wherein silver oxide (AgO) is formed at the interface with the electrolyte.

9. The apparatus according to any one of claims 5-8, wherein the cathode is exposed to ambient air.

10. The apparatus of claim 1, wherein the ions migrating in the electrolyte are H+. + and OH - The device comprises: - Cathode, which consists of silver and embedded OH - Made of ionic materials, and - The anode is made of a material containing an M2B3O7-type structure, where M is an alkali metal or a mixture of alkali metals, B is titanium, and O is oxygen for embedding H. + ion.

11. The apparatus of claim 1, wherein the ions migrating in the electrolyte are H+ ions. + and OH - The device comprises: - Cathode, which consists of silver and embedded OH - Made of ionic materials, and - Anode, which consists of graphite and embedded H + It is made of ionic materials.

12. The apparatus of claim 1, wherein x = 0 and M and / or N comprises at least one element selected from sodium and lithium, the apparatus comprising: - The anode, which is made of a material containing sodium and lithium respectively, and - Cathode, which allows the inclusion of lithium and / or sodium ions.

13. The apparatus of claim 12, wherein the cathode is made of a material selected from graphite and M'2B3O7 type structure, wherein M' is an alkali metal or a mixture of alkali metals, B is titanium, and O is oxygen, for embedding and migrating M+ and / or N+ ions.

14. The apparatus according to any one of the preceding claims, wherein the anode material and the electrolyte material are continuously deposited in the form of their respective thin layers.

15. The apparatus according to any one of the preceding claims, wherein at least the anode is encapsulated in a resin-based material, thereby being sealed to prevent air and moisture.

16. The device according to any one of the preceding claims, wherein the entire device is encapsulated in a resin-based material, thereby being sealed to prevent air and moisture.

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