Battery having improved electrolyte and improved electrode

Abstract

This description relates to a battery element comprising the following: - Electrodes including an anode and a cathode, and - An electrolyte comprising a crystalline material having the composition M2B2O5.x(HOH).y(NOH) between the electrodes. Here, M and N are alkali metals or hydrogen or a mixture of alkali metals or hydrogen, B is titanium, O and H represent elemental oxygen and hydrogen, respectively, and x and y are between 0 and 4 and indicate the presence of H+, OH-, and N+ ions that can move within the crystalline material. In particular, at least one type of ion among H+, OH-, N+, and M+ is mobile to move toward at least one of the electrodes within the crystalline material, and at least one of the electrodes is made of a material suitable for performing chemical interactions with at least one of the H+, OH-, N+, and M+ ions.

Description

Technology Field

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

[0002] Document WO-2018 / 060656 presents a particularly promising material for forming the electrolyte of a supercapacitor, which is a crystalline solid having an A2B2O5 structure, where A can be an alkali metal and B can be titanium. The performance of this material led the inventors specified in the document to consider its application in batteries, which is mentioned in the document (specifically, page 12, lines 15-30, see Figure 8 of the document).

[0003] However, the purpose of the presented embodiment was to regard the entire electrolyte in contact with the two electrodes as a "pseudo-battery" in the sense that electrical discharge ("rapid on the order of a few minutes, followed by relatively slow on the order of several hours") could not be perfectly controlled, and jackets of piezoelectric elements such as PZ1, PZ2, and PZ3 were still required to mechanically restrain or relax the material to cut off or release electric charge.

[0004] Typically, the material provided for the electrode was simply carbon to collect electrons, or a metal such as copper, silver, gold, or platinum. The problem to be solved

[0005] The present disclosure improves the situation.

[0006] The present disclosure proposes improving the material selected for the electrode by generating controlled chemical interactions between ions that can move within the electrode material and the electrolyte material, while maintaining similar materials for the electrolyte, in order to better manage the charge / discharge of the device and increase the energy density that can be stored. means of solving the problem

[0007] Therefore, the objective is a battery element comprising the following:

[0008] - Electrodes including an anode and a cathode, and

[0009] - An electrolyte comprising a crystalline material having the composition M2B2O5.x(HOH).y(NOH) between the electrodes, wherein M and N are alkali metals or hydrogen or a mixture of alkali metals or hydrogen, B is titanium, O and H represent elemental oxygen and hydrogen, respectively, and x and y are between 0 and 4 and represent H capable of migrating in the crystalline material. + , OH - , N + Indicates the presence of ions.

[0010] The above H + , OH - , N + and M + At least one of the ions is mobile to move toward at least one of the electrodes within the crystalline material, and at least one of the electrodes is the H + , OH - , N + and M + It is a device made of a material suitable for performing a chemical interaction with at least one of the ions.

[0011] As used above, "chemical interaction" is understood to mean the intercalation of ions moving toward the electrode, or the chemical reaction between these ions and the electrode material. Accordingly, the aforementioned chemical interaction includes one of the following:

[0012] - The above H + , OH - , N + and M + Intercalation of at least one of the ions to at least one of the electrodes, and

[0013] - The above OH - , N + and M + Chemical (typically electrochemical) reaction with at least one material of at least one of the electrodes, of at least one of the ions.

[0014] In the device described in the aforementioned document WO-2018 / 060656, moving ionic species accumulated near the electrodes to generate charge accumulation, which enabled the collection, storage, and release of electrical energy, but in a purely electrostatic form. Therefore, the amount of energy stored in the device constructed according to the teachings of document WO-2018 / 060656 remained limited by the electrostatic nature of the storage.

[0015] Here, chemical interaction with the electrode enables more efficient control of charging / discharging and increases energy storage density.

[0016] The prior art cited above did not assume that the electrode could be composed of a material that undergoes ion-intercalating or electrochemical reactions with migrating ionic species. Therefore, migrating species within the electrolyte (particularly OH) - , H + , O 2-It did not consider that ) could chemically react with the constituent material of the electrode or intercalate into it.

[0017] According to the present embodiment, the battery device of the present description is endowed with microscopic faradaic mechanisms typically present in the design of secondary batteries, primary batteries, or fuel cells, thereby enabling fine control of the charging or discharging of such devices. More specifically, the energy density is improved by adding mechanisms of intercalation, ion absorption, or electrochemical reaction at the electrode surface used, as well as by expanding the selection of mobile species within the electrolyte. Subsequently, the selection of the electrode constituent material is made to adapt to the mobile species within the electrolyte to create a secondary battery device, a primary battery, or a fuel cell.

[0018] Solid electrolytes may be in the form of single crystals, ceramics, pressed powders, membranes, or thin films. Its 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 may be equal to 0. For brevity, this electrolyte material is referred to as "MTO" below.

[0019] The electrode material may be in solid, liquid, or gaseous form as described below.

[0020] In a typical embodiment, the battery element is a moving OH - For chemical reactions with ions, an anode made of a material containing a metal hydride may be included.

[0021] Alternatively, the anode is a moving OH. -For chemical reactions with ions, it may be made of a material containing at least one of zinc, iron, and aluminum (or sodium or lithium).

[0022] As another alternative, the anode is a mobile OH. - For chemical reactions with ions, it can be made of a material containing dihydrogen.

[0023] As for the cathode, it may contain a mixture of oxygen and water.

[0024] For example, the cathode can be made of a material containing nickel oxide hydroxide (NiOOH).

[0025] Alternatively, the cathode may contain silver oxide (AgO).

[0026] In this embodiment, the cathode may initially be made of a material containing silver (Ag), and then silver oxide (AgO) may be formed at the interface with the electrolyte, which is typically in accordance with the embodiment further described below with reference to FIG. 6 when the cathode is exposed to ambient air (particularly to provide the aforementioned mixture of oxygen and water).

[0027] In one specific embodiment, the device is H moving within the electrolyte. + and OH - It can utilize ions and includes the following:

[0028] - Contains silver and OH - A cathode made of a material that intercalates ions, and

[0029] - H + An anode made of a material having an M2B3O7 type structure for ion intercalation. Here, M is an alkali metal or a mixture of alkali metals, B is titanium, and O is oxygen.

[0030] Alternatively, the device may include the following:

[0031] - Contains silver and OH - A cathode made of a material that intercalates ions, and

[0032] - Contains graphite and H + An anode made of a material that intercalates ions.

[0033] As another alternative, in a battery element where x=0 and M and / or N comprises at least one element selected from sodium and lithium, the element may comprise the following:

[0034] - An anode made of a material containing one of the elements of sodium and lithium (e.g., in metallic form), and

[0035] - A cathode that allows the incorporation of lithium and / or sodium ions.

[0036] For example, such a cathode is a moving M + and / or N + To intercalate ions, it can be made of a material selected from graphite and a M'2B3O7 type structure (where M' is an alkali metal or a mixture of alkali metals, B is titanium, and O is oxygen).

[0037] In one or more of the embodiments described above, the anode material and the electrolyte material can be deposited sequentially in the form of respective thin films (this embodiment is typically easy to implement when the anode is made of a material having an M2B3O7 structure).

[0038] In one or more of the embodiments described above, at least the anode is encapsulated with a resin-type material or an equivalent material so as to be sealed against air and moisture.

[0039] In addition, the entire device (anode, electrolyte, and cathode) can be encapsulated in a resin-type material or an equivalent material to be sealed against air and moisture.

[0040] It is possible to produce a so-called "all-solid-state" battery when the electrode material is in a solid form, or when one of the electrodes consists simply of ambient air (e.g., the cathode in some of the embodiments described above).

[0041] More generally, the selection of materials for the anode and cathode can be made as follows: the standard redox potential (E0a) of the couple at the anode must be lower than the standard redox potential (E0c) of the couple at the cathode. Depending on the selection of the electrodes, it is possible to classify the examples by the characteristics of the transported species in the electrolyte.

[0042] OH - In one embodiment utilizing ion transport, the electrolyte material utilizes highly mobile hydroxide ions (OH) through spontaneous hydration. - It will generate ).

[0043] In this case, for example, to manufacture a secondary battery, it may be advantageous to select the following:

[0044] - Metal hydrides (such as MgH2) as anode materials, and

[0045] - Nickel oxyhydroxide (NiOOH) as a cathode material.

[0046] To manufacture other types of batteries:

[0047] - Metals such as zinc (or iron or aluminum, or a mixture) can be used in the anode, and

[0048] - Silver oxide (AgO) or a mixture of O2 and H2O can be used as the cathode material.

[0049] To manufacture fuel cells:

[0050] - Dihydrogen can be used as an anode material, and

[0051] - A mixture of O2 and H2O can be used as the cathode material.

[0052] In addition, hydroxide ions OH - and hydrogen ions H + It is possible to generate a combined migration of all, which can be used to an advantage.

[0053] In fact, by incorporating oxygen vacancies into the structure of the electrolyte material, water vapor H + and OH - It is possible to induce dissociation. Since these two species can move independently of each other, the following electrode selection is possible.

[0054] For example, a silver (Ag) cathode is typically OH - It can react electrochemically with ions. At the anode, by graphite-based compounds, or by solid materials similar to electrolyte materials such as A2Ti3O7 where A can be an element among sodium Na, potassium K, or rubidium Rb, or H + H by any type of material capable of intercalating + Ion intercalation or electrochemical reactions can be ensured.

[0055] This embodiment has the advantage of forming a cathode by growing a first electrode (anode), e.g., K2Ti3O7, having proton intercalation properties on a suitable substrate, then growing a solid electrolyte, e.g., K2Ti2O5, which is easy to grow on the anode considering the similarity of the crystalline phase (and e.g., lattice matching), and finally growing an Ag or graphite layer on the solid electrolyte that does not cause deposition or interface problems.

[0056] This design makes it possible to solve a frequently occurring problem in the field of all-solid-state batteries regarding the quality of the electrode / electrolyte interface when the two materials have very different crystallographic structures.

[0057] Na present in electrolytes + The movement of other species, such as [the same], can also be utilized.

[0058] By adding sodium to the chemical formula of MTO, for example, highly mobile Na within their structure + A2B2O5(NaOH) or A containing ions 2-x Na x Obtain B2O5 material.

[0059] Therefore, in the case of secondary batteries:

[0060] - The anode material may contain metallic sodium, and

[0061] - The cathode material is a graphite-based compound, or A2Ti3O7 or Na2Ti3O7 where A can be [Na, K, Rb]. + It may include other types of materials capable of intercalation.

[0062] Depending on the moving ion species, other embodiments are, of course, possible. For example, lithium ion Li + To utilize the migration of, by adding lithium to the chemical formula of the electrolyte material, A2B2O5(LiOH) or A 2-x Li x It is possible to obtain B2O5 materials, each of which has high mobility Li within its structure + It holds ions.

[0063] For secondary batteries, the following can be used in the same way:

[0064] - Metallic lithium as an anode material, and

[0065] - As a cathode material, a graphite-based compound, or A2Ti3O7 or Li where A can be [Na, K, Rb]. +Other types of materials capable of intercalating. Brief explanation of the drawing

[0066] Other features, details, and advantages will become clear by reading the detailed description below and reviewing the following attached drawings: Figure 1 shows the crystallographic structure of an MTO electrolyte material according to one embodiment. Figure 2 shows the incorporation of water molecules into this material. Figure 3 shows the gain in thermodynamic energy as a function of the hydration percentage of sites within the material structure, proving that the more water molecules there are, the more stable it is. Figure 4 shows a comparison between the electrode arrangements in the "parallel" configuration (left figure) and the "transverse" configuration (right figure) of the material. FIG. 5 shows a battery-type device in which the electrolyte is based on the aforementioned MTO material according to one embodiment. Figure 6 shows an example of such a device in which the electrodes are based on zinc and silver (oxidized at the interface with the electrolyte). FIG. 7 shows an element according to the prior art in the sense of WO-2018 / 060656, comprising identical electrodes made of gold in this exemplary embodiment. Figure 8 shows a comparison of the electrical performance of the devices of Figures 6 and 7. Specific details for implementing the invention

[0067] The use of materials of the M2Ti2O5 family (or hereinafter "MTO") as solid electrolytes for all-solid-state energy storage devices is described below, wherein M = [Li, Na, K, Rb, H...] or combinations of these elements such as Rb2Ti2O5 and K2Ti2O5 (particularly having a structure similar to that described in document WO-2018 / 060656). More generally, M2Ti2O5 where x is 2 or greater and M = [Li, Na, K, Rb] x O 2x+1 A family of compounds having the formula is considered here to provide these properties.

[0068] At the microscopic level, the MTO material is Ti2O5 2- and Rb2 2+ It is characterized by a lamellar structure with ionic bonds between planes. The material is layered and can be cleavable along planes located between Rb atoms.

[0069] Non-hydrated or weakly hydrated materials are H according to the chemical formula of the compound + , K + , Rb + , Na + , Li + It can conduct ionic species such as, for example, (Na,K)2Ti2O5, which can combine various cations in its composition.

[0070] In addition, there is the potential provided by hydrated MTO materials, which are actually highly hygroscopic and possess the characteristic of spontaneously adsorbing water vapor, particularly in powder form. Ab initio simulations using density functional theory showed that this molecular water preferentially organizes into channels along the crystallographic b-axis direction. As illustrated in Figures 1 and 2, water is incorporated into the structure by forming hydrogen bonds with the apical oxygen atoms of the perovskite structure, which corresponds to the most promising configuration according to the simulations.

[0071] In this composition, the addition of water molecules represents an energy change of -0.5 eV (PBEsol method) or -0.25 eV (HSE method) at T=0.

[0072] Figure 1 illustrates the insertion of water molecules into the molecular structure of a material containing an Rb atom (one atom is shown in the upper right of Figure 1), an oxygen atom O (one atom is shown in the center of Figure 1), hydrogen atoms H (two of which are shown to the right of the central oxygen atom in Figure 1), and a titanium atom Ti (lower right of Figure 1), which creates very strong hydrogen bonds. This structure, having the general formula MTO, is referred to here more specifically as "RTO" because the M atom in the general MTO formula is an Rb atom. Thus, Figure 1 illustrates the incorporation of water molecules into an RTO (or more generally MTO) structure, creating two very short hydrogen bonds with the terminal oxygen atoms 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 (exemplified in Figures 2 and 3, which will be discussed later), which favors the creation of chains of water molecules, which can lead to a Grotthus-type proton conduction mechanism, particularly in water.

[0073] More generally, entities moving within intercalated water may be one of the following species: OH - and / or M + (where M = [H, Li, Na, K, Rb]) and / or O 2- .

[0074] The hydrophilic properties of MTO promote water absorption.

[0075] For an MTO material where M=Rb, as exemplified in FIG. 2, water molecules are arranged in the MO plane (where O1 designates the terminal oxygens of the structure). The molecules self-organize into chains (channel formation) in the ab plane, preferentially oriented so that the ab plane is parallel to the deposition substrate (referred to as "parallel" orientation), or the ac plane is oriented parallel to the substrate plane (referred to as "transverse" orientation). This is exemplified on the left and right of FIG. 4, respectively, where the lines represent the ab plane of the layered compound.

[0076] Characteristically, Figure 3 shows the thermodynamic energy gain at temperature T=0 as a function of the hydration percentage of sites within the structure.

[0077] The aforementioned MTO material can subsequently be used as a solid electrolyte (and thus an ion conductor) and can be used in micrometer or nanometer, planar and crystalline configurations, for example, in which the electrolyte consists of an MTO thin film deposited on a substrate S, such as an integrated circuit, using deposition techniques such as PVD (physical vapor deposition) or CVD (chemical vapor deposition), including sputtering, pulsed laser deposition, atomic layer deposition, molecular-beam epitaxy, reactive plasma deposition, etc. The MTO layer is preferably single-crystalline and / or regionally microcrystalline.

[0078] Alternatively, the electrolyte can consist of an MTO thin film obtained by exfoliating sheets from millimeter-sized crystals. These sheets, with a nanometer thickness (up to several hundred nm), can then be transferred to an integrated circuit, where they naturally adopt a parallel orientation.

[0079] Referring to Fig. 5, in these two cases, electrodes A and B are deposited on each side of the MTO thin film in the case of parallel orientation, or on the top and bottom of the layer in the case of transverse orientation (using vacuum deposition technology), so that ion conduction occurs preferentially in the ab crystallographic plane (bidirectional arrow in Fig. 5).

[0080] A controlled hydration step of the thin film can be implemented before and after electrode deposition and, if possible, before an encapsulation step. Finally, an encapsulating agent E (e.g., silicone, epoxy resin, or conformal coating, polyurethane compound, etc.) can be deposited over the entire surface to "freeze" the selected hydration level.

[0081] Alternatively, the electrolyte may consist of MTO in bulk and crystalline forms, and thus may be composed of one or more oriented single crystals (stacked perpendicular to the ab crystallographic plane) and aggregated together within a polymer matrix (epoxy resin, silicone, or polyurethane compound). A controlled hydration phase of the crystals may be implemented prior to encapsulation within the matrix.

[0082] As illustrated by the bidirectional arrow in Fig. 5, two electrodes A and B are deposited on both sides of an encapsulated single crystal so that ion conduction occurs in the crystallographic ab plane.

[0083] Alternatively, for the fabrication of bulk devices, MTO infused with an encapsulating agent may be used, and the MTO material may have a crystalline form such as a membrane or ceramic. For example, the electrolyte may consist of MTO crystals mixed with at least one organic or aqueous solvent (e.g., 2-methylpyrrolidinone, water, ethanol, etc.). To increase the mechanical stability of the device, a fluorinated compound dispersed in the solvent (e.g., polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), etc.) may also be added. The size of the MTO crystals may vary from several millimeters to several hundred nanometers. The volume percentage of MTO may be between 60% and 98% depending on the selected solvent. A controlled hydration step may be considered before mixing the powder with the solvent used. Depending on the solvent selected for the fabrication of the device, the mixing process may be extended over tens of hours and may include an annealing step at a temperature of up to 150°C. Depending on the intended application, the mixture may then be deposited on a non-adhesive substrate (such as a Teflon film) or on an electron-collecting electrode capable of interacting with ions (e.g., zinc, gold, silicon, sodium and / or lithium (which are metallic), or silver oxide AgO, etc.), which is described in detail below.

[0084] To this end, the deposition method may include, for example, inkjet printing, spin coating, or doctor blade coating. Subsequently, the drying step may take tens of hours at a temperature that can reach up to 150°C. After the solvent evaporates, a film having a thickness ranging from several micrometers to several millimeters is obtained. Then, if the film is deposited on one electrode, another electrode may be deposited on top of the film. If the film is deposited on a non-adhesive substrate, two electrodes are deposited, one on each side of the film. The film and its electrodes may then be encapsulated, and the encapsulation provides excellent mechanical strength as well as sealing against air and moisture.

[0085] In one embodiment, the electrolyte consists of an MTO ceramic compressed to 10 tons at 150°C for 2 hours and sintered at 800°C for 10 hours. Alternatively, 2 to 5% of the mass fraction of PTFE (polytetrafluoroethylene) may be added to the MTO powder to make the ceramic stronger without the sintering step. The electrode is then deposited using a polymer-solvent-material mixture (8% PVDF: polyvinylidene fluoride - 84% solvent: 1-methyl-2-pyrrolidinone - 8% material) and then dried at a temperature between 25 and 80°C for several hours. It is also possible to place the constituent powders for electrodes A and B into a press system to manufacture the electrodes simultaneously with the ceramic.

[0086] The selection of possible electrodes for the different geometric structures of the energy storage devices described above should be based on the mobile species within the electrolyte and the type of selected device. In the considered configuration, the MTO material has a standard redox potential E0 a An anode composed of a material having and standard redox potential E0 cIt is used as a solid electrolyte disposed between cathodes composed of a material having, where E0 a < E0 c am.

[0087] Various examples for fabricating anodes and cathodes are presented below. Asymmetry can be created between the cathode and anode by encapsulating one of the electrodes and leaving the other electrode "exposed to air," which creates the possibility of supplying oxygen or water vapor to the device from only one side and results in a supercapacitor effect.

[0088] OH - Ion conduction can be utilized in (non-rechargeable) "metal-air" battery configurations. Materials that can be used as anodes include, for example, metallic zinc (Zn), metallic iron (Fe), metallic aluminum (Al), or metal alloys composed of at least two of the materials mentioned above.

[0089] An example of a redox reaction occurring at the anode is as follows:

[0090] Zn + 2 OH - ZnO + H2O + 2 e -

[0091] Materials that can be used as a cathode include, for example, the following:

[0092] - Silver oxide: AgO, or

[0093] - N2 / O2 / H2O gas mixture: Typically, ambient air may be used (humidity levels greater than 5% and less than 95%, oxygen (O2) levels greater than 15% and less than 25%, nitrogen (N2) levels greater than 75% and less than 85%), and some examples of redox reactions occurring at the cathode may be as follows:

[0094] O2 + 2 H2O + 4 e - 4 OH -

[0095] AgO + H2O + 2 e - Ag + 2 OH -

[0096] Other embodiments may utilize NiMH (nickel-metal hydride) battery configurations. Materials that can be used as an anode include, for example, the following:

[0097] - For example, AB_5 type alloys based on rare earth elements (La, Ce, Nd, Pr), such as LaNi5 and its derivatives, or alloys containing elements among Ni, Co, Mn, Al, Mg, Zr, C, Co, Fe, and Ti.

[0098] An example of a redox reaction occurring at the anode may be as follows:

[0099] OH + MH H2O + M + e, where M is a metal element that originally exists in the form of metal hydride MH (e.g., TiH2 or MgH2).

[0100] Materials that can be used as a cathode include, for example, the following:

[0101] - Nickel oxyhydroxide (NiOOH), or

[0102] - A mixture of metal oxides (Ni-Co-Mg), or

[0103] - Ni-Co-Al alloy.

[0104] An example of a redox reaction occurring at the cathode may be as follows:

[0105] NiO(OH) + H2O + e - Ni(OH)2+ OH -

[0106] To utilize proton conduction, materials that can be used as an anode (negative electrode) may include, for example, the following:

[0107] - WO3, MoO3, TiO2, H2Ti3O7, H2Ti6O13 , H2Ti 12 O 25 and other derivatives by substitution.

[0108] Materials that can be used as the cathode (anode) may include, for example, the following:

[0109] - Metal oxides: RuO2, MnO2, V2O5, PbO2

[0110] - Protonated metal oxide: HCoO2

[0111] - Prussian Blue Analog ("PBA") material, for example, A x M[Fe(CN)6] y .zH2O

[0112] - Or organic materials, for example, PEDOT or HATN.

[0113] Li + To utilize ion conduction, materials that can be used as an anode (negative electrode) are, for example, as follows:

[0114] - Graphite carbon derivatives: carbon nanotubes, graphene, mesoporous carbon, etc.

[0115] - Metallic lithium (Li).

[0116] Materials that can be used to form the cathode (anode) may be, for example, as follows:

[0117] - Lithium-oxidized metal oxides, e.g., LiCoO2

[0118] - Lithium intercalation compounds (e.g., mixtures of metal oxides (Ni-Co-Mg), Ni-Co-Al alloys, PBA Prussian blue structural materials, etc.).

[0119] Na + Materials that can be used to form an anode (negative electrode) to utilize ion conduction are, for example, as follows:

[0120] - Carbon derivatives (graphite, carbon nanotubes, graphene, mesoporous carbon, etc.),

[0121] - Metallic sodium (Na),

[0122] - Sodium alloys: Sodium-tin (Na-Sn), sodium-lead (Na-Pb), sodium-bismuth (Na-Bi),

[0123] - Alloys of sodium and intercalated transition metals: Na-Mn-O, Na-Cr-S, Na-Ti-S,

[0124] - Tin-based compounds: SnO2, SnSb,

[0125] - Na2Ti3O7 and Na4Ti5O, which belong to the family of electrolyte materials and can be deposited as solid thin films 12 , layered titanium oxide of the NaTi2(PO4)3 type,

[0126] - Vanadium or sodium oxide: NaV2O5

[0127] Materials that can be used for the cathode (anode) are, for example, as follows:

[0128] - Structural materials such as Prussian Blue PBA,

[0129] - TiSe2

[0130] - Sodium iron phosphate or sodium nickel phosphate: NaFePO4, NaNiPO4

[0131] - Sodium manganese oxide: NaMnO2

[0132] - Sodium nickel manganese oxide: Na(NiMn)O2

[0133] - Sodium cobalt oxide or sodium chromium oxide: NaCoO2, NaCrO2

[0134] - Sodium-nickel-cobalt oxide: Na(NiCo)O2

[0135] - Sodium copper oxide: NaCuO2.

[0136] Comparative examples

[0137] FIG. 6 illustrates an example of a device according to the present description, wherein:

[0138] - The electrolyte comprises an MTO material obtained by starting from a single crystal or a compressed polycrystalline material in a solvent, drying it, and then implementing the aforementioned method between two electrodes.

[0139] - The anode is made of a zinc (Zn)-containing material and is encapsulated in resin E to prevent oxidation, and

[0140] - The cathode is initially made of a material containing silver (Ag) but is not encapsulated, so the silver oxidizes spontaneously in the atmosphere and upon contact with MTO, so the cathode material actually becomes silver oxide (AgO), and the remainder of the initial Ag material serves to efficiently conduct charge to the cathode wire Fc (which is made of silver, similar to the anode wire Fa).

[0141] A device according to the prior art (Fig. 7) was manufactured under strictly identical conditions, where:

[0142] - The electrolyte comprises MTO material obtained under the same conditions (starting from a single crystal or compressed polycrystalline material in a solvent, then dried, between two electrodes), and

[0143] - The anode and cathode are made of the same material containing gold (an excellent conductor but blocks ions), the anode is encapsulated in resin E so as to be under the same experimental conditions as the device in Fig. 6, and the anode and cathode wires are made of silver as above.

[0144] The embodiment according to FIG. 6 is an OH that chemically reacts with a Zn anode according to the following type of equation. - Utilizes ion movement:

[0145] Zn + 2 OH - ZnO + H2O + 2 e -

[0146] At an AgO cathode, since the surrounding air naturally contains water vapor H2O and oxygen O2, the chemical equation is of the following type:

[0147] O2 + 2 H2O + 4 e - 4 OH

[0148] AgO + H2O + 2 e - Ag + 2 OH -

[0149] Figure 8 illustrates a comparison of the results and shows the cyclic voltammetry curves of the elements in Figures 6 and 7.

[0150] The device in Fig. 6 shows significant improvement compared to the prior art device (Fig. 7). In Fig. 8, the redox peak (dotted curve) indicates the presence of an electrochemical reaction controlling the charging and discharging of the device. Capacitance is improved tenfold and energy density is improved twentyfold. Furthermore, the reversibility observed during the electrical discharge / charging of the device makes it an ideal candidate for the manufacture of secondary batteries.

[0151] The performance of the device described in this specification can be further enhanced through very thin layers of stackable electrodes and electrolytes, thereby enabling improved performance per unit area of ​​the device and greater densification.

Claims

Claim 1 A battery element comprises: electrodes including an anode and a cathode; and between the electrodes, an electrolyte comprising a crystalline material having the composition M2B2O5.x(HOH).y(NOH), wherein M and N are alkali metals or hydrogen or a mixture of alkali metals or hydrogen, B is titanium, O and H represent elemental oxygen and hydrogen, respectively, and x and y are between 0 and 4 and H is mobile in the crystalline material. + , OH - , N + Indicates the presence of ions, and the above H + , OH - , N + and M + At least one ion is movable to move toward at least one of the electrodes within the crystalline material, and at least one of the electrodes is the H + , OH - , N + and M + A device made of a material suitable for performing a chemical interaction with at least one of the ions. Claim 2 In paragraph 1, the moving OH - A device comprising an anode made of a material containing a metal hydride for chemical reaction with ions. Claim 3 In paragraph 1, the moving OH - A device comprising an anode made of a material containing at least one element among zinc, iron, and aluminum for chemical reaction with ions. Claim 4 In paragraph 1, the moving OH - A device comprising an anode made of a material containing dihydrogen for chemical reaction with ions. Claim 5 In any one of the prior claims, the device wherein the cathode comprises a mixture of oxygen and water. Claim 6 A device according to any one of the prior claims, wherein the cathode is made of a material comprising nickel oxyhydroxide (NiOOH). Claim 7 A device according to any one of claims 1 to 5, wherein the cathode comprises silver oxide (AgO). Claim 8 A device according to claim 7, wherein the cathode is made of a material containing silver (Ag), and silver oxide (AgO) is formed at the interface with the electrolyte. Claim 9 A device in which, in any one of paragraphs 5 to 8, the cathode is exposed to ambient air. Claim 10 In claim 1, the ion moving within the electrolyte is H + and OH - and, - contains silver and OH - A cathode made of a material that intercalates ions, and - H + A device for intercalating ions comprising an anode made of a material having an M2B3O7 type structure, wherein M is an alkali metal or a mixture of alkali metals, B is titanium, and O is oxygen. Claim 11 In claim 1, the ion moving within the electrolyte is H + and OH - and, - contains silver and OH - A cathode made of a material that intercalates ions, and - containing graphite and H + A device comprising an anode made of a material that intercalates ions. Claim 12 A device according to claim 1, wherein x=0 and M and / or N comprise at least one element selected from sodium and lithium, - an anode made of a material comprising one of sodium and lithium, respectively, and - a cathode that allows the incorporation of lithium and / or sodium ions. Claim 13 In Clause 12, the M in which the above cathode moves + and / or N + A device for intercalating ions, made of a material selected from graphite and a M'2B3O7 type structure, where M' is an alkali metal or a mixture of alkali metals, B is titanium, and O is oxygen. Claim 14 A device in which, in any one of the prior claims, the anode material and the electrolyte material are each deposited in the form of thin films. Claim 15 A device in which, in any one of the prior claims, at least the anode is encapsulated in a resin-type material so as to be sealed against air and moisture. Claim 16 In any one of the prior claims, the device is encapsulated in a resin-type material so that the entire device is sealed against air and moisture.

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