Solid-state battery and method for manufacturing the battery

Abstract

The invention relates to a method for manufacturing a liquid-electrolyte-free battery and / or a solid-state battery, the method comprising: providing a cathode mix of components containing a cathode active material and a reagent, said mix of components preferably providing at least the constituents of a cathode, and said mix of components containing at least one conductive material; providing an anode and inducing in-situ formation of a passivation layer functioning as a separator between the anode and the cathode. The invention further relates to a battery and an assembly for manufacturing a battery.

Description

[0001] A solid-state battery and a method of manufacturing the battery

[0002] Technical field

[0003] The present invention relates to a novel method for preparing a battery, the battery obtained by the method, and a battery without liquid electrolyte and / or a solid-state battery. The invention also relates to the battery and an assembly for assembling the battery.

[0004] State of the art and problems giving rise to the invention

[0005] In many ways, electrical energy represents the most interesting form of energy because it can be converted into other forms of energy relatively easily.

[0006] For several reasons, electrical energy production in most cases does not coincide with current energy needs. Indeed, electrical energy consumption is subject to consumers' daily habits and circadian rhythms and also varies seasonally. Second, in mobile electrical applications, such as electric vehicles, stored electrical energy is required. Finally, more and more devices are powered by batteries. For these reasons, among others, batteries are attracting increasing interest.

[0007] Batteries are devices containing components capable of generating electrical energy through electrochemical reactions that take place within the battery, for example, when it is connected to an external electrical circuit. More generally, batteries are devices for storing electrical energy.

[0008] Lithium batteries are widely available commercially. They can consist of an anode, an electrolyte, a separator, a cathode, two metal current collectors, and a metal casing. The anode is usually made of carboxymethylcellulose polymer filled with graphite powder. The cathode is usually made of PVDF polymer filled with metal oxide, such as lithium-nickel-manganese-cobalt oxide or lithium-iron-phosphate, and SP carbon. The separators are usually made of a thin, porous plastic polymer film. The electrolytes are usually made of non-aqueous electrolyte with a dissolved lithium salt. The current collectors are usually made of aluminum foil and copper foil. The metal casings or shields in which all the elements listed above are packaged are usually made of aluminum or stainless steel.Current challenges for lithium batteries include lifespan, energy capacity, safety, and reducing manufacturing costs. Another objective of the present invention is to limit toxic waste and reduce overall environmental impact, such as CO2 emissions and raw material usage.

[0009] A new class of lithium batteries has been studied over the past few decades for commercial application to replace the non-aqueous electrolyte of lithium batteries. These are solid-state batteries that use a solid electrolyte instead of a non-aqueous liquid electrolyte. The all-solid-state battery has the advantage of being safer than the liquid electrolyte used in lithium batteries, which prevents the battery from catching fire. Therefore, there is no need for safety components. In addition, this approach allows the use of a lithium metal anode, allowing for higher capacity. Finally, it allows for higher gravimetric and specific energy density. However, there is still a need to simplify integration for manufacturing, increase their cycle life, and reduce the cost of large-scale all-solid-state batteries.

[0010] US 3,937,635 discloses a battery comprising a lithium anode and a cathode comprising an iodine source. A separator is placed between the anode and the cathode, and a lithium iodine electrolyte spontaneously forms on the surface of the anode during assembly. However, this battery requires a relatively large number of different parts and layers.

[0011] WO 2017 / 023884 A1 discloses a battery comprising a cathode of elemental iodine, an anode comprising lithium or metallic silver, and iodide between the anode and the cathode serving as a separator and electrolyte. The formation of silver iodide on the surface of the metallic silver has been observed. The entire battery can be formed, including the iodine cathode, from a mixture of silver iodide and lithium iodide in the presence of an external potential applied to current collectors.

[0012] R. Brodd, "Batteries, 1977 to 2002" discloses under the title "Medical Lithium Batteries" a Li-L type battery, made by preparing a mixture of elemental iodine (I2) and poly(24-vinyl)pyridine (PVP). When the mixture is heated to a high temperature and melted, a conductive material is formed. The molten mixture is deposited on the surface of a lithium anode.

[0013] WO 2018 / 231731 discloses semi-solid-state, solid-state, and fuel cell batteries. Furthermore, this document discloses obtaining an electrolyte by contacting the anode with an ionic conductor and adding a separate cathode once an SEI is formed.

[0014] An objective of the invention is to produce a primary or secondary battery in a simple manner, at an advantageous cost, and preferably a battery without liquid electrolyte. Such a battery would avoid the disadvantages of liquid electrolyte batteries.

[0015] Another objective of the invention is to produce a battery based on non-toxic materials, for example a compostable battery.

[0016] Another objective of the invention is the implementation of a platform and / or a generalized approach that can be applied with different types of redox species and / or metal cations, for example.

[0017] An objective of the invention is to implement a battery in which the use of a current collector is not mandatory in all cases, depending on the metal and / or cation used.

[0018] Summary of the invention

[0019] In one aspect, the present invention relates to a method for manufacturing a liquid electrolyte-free battery and / or a solid-state battery, the method comprising: providing a cathode mixture of components comprising a cathode active material and a reactive agent, said mixture of components preferably providing at least the constituents of a cathode, and said mixture of components comprising at least one conductive material; providing an anode; inducing the in situ formation of a passivation layer functioning as a separator between the anode and the cathode.

[0020] In one aspect, the present invention relates to a battery which can be obtained by the method according to the invention.

[0021] In one aspect, the present invention relates to a liquid electrolyteless battery and / or a solid-state battery comprising a cathode, an anode, and a solid-electrolyte interface (SEI) separator, said SEI preferably being formed in situ.

[0022] In one aspect, the present invention relates to an assembly for assembling a battery, the assembly comprising an anode and a cathode mixture of components comprising a cathode active material and a reactive agent, said mixture of components preferably providing at least the constituents of a cathode.

[0023] In one embodiment, said mixture of components comprises at least one conductive material, characterized in that a cation chosen from the cations of magnesium, iron, zinc, aluminum, nickel, lithium, sodium, potassium, calcium, manganese, indium, vanadium, zirconium, lanthanum, boron, silicon, cobalt, tin, titanium, hydrogen, and / or an anion chosen from the anions of oxygen, sulfur, phosphate, chloride, fluoride, iodide, bromide, sulfate, acetate, nitrate, and organic anions is present in the mixture of components, preferably in said reactive agent, said assembly allowing the preparation of a battery following the contacting of the anode with a cathode formed from said cathodic mixture of components.

[0024] Other aspects and preferred embodiments of the invention are defined in the claims and description below.

[0025] Description of the drawings

[0026] The characteristics and advantages of the invention will appear more clearly on reading a non-limiting description of three preferred embodiments. This description is given solely by way of example, and made with reference to the schematic figures in which:

[0027] Figure 1A is a schematic view of an anode and a cathode before assembly of the battery according to a first embodiment. Figure 1B is a schematic view of the battery of Figure 1A following assembly of the anode and the cathode and the in situ formation of a separator and / or solid electrolyte.

[0028] Figure 2 is a schematic view of a battery according to another embodiment.

[0029] Figure 3 is a schematic view of a button cell battery according to yet another embodiment.

[0030] Detailed Description of Preferred Embodiments

[0031] The present invention relates to a method for manufacturing a battery, as well as to a battery obtainable, for example, by the method. The method also relates to a frame and / or assembly generally enabling a battery to be prepared according to a generalizable design and based on a wide selection of constituents. The invention also relates to a battery.

[0032] The method comprises providing an anode. In one embodiment, the anode comprises one or more selected from a metal in its metallic form, graphite, hard carbon, activated carbon, a metal alloy, a metal oxide, a polyanionic compound such as phosphate-based compounds, sulfate-based compounds and a combination of several of the above materials.

[0033] In one embodiment the anode of the battery comprises magnesium, preferably magnesium metal.

[0034] In one embodiment, the anode of the battery comprises one or more chosen from lithium, sodium, calcium, iron, zinc, manganese, aluminum, preferably in metallic form.

[0035] The anode may comprise and / or form an insertion material, allowing a metal to be accommodated and / or metal cations to be received. Examples of insertion materials are graphite (e.g. metallized graphite), hard carbon (metallized hard carbon), a metal, a metal alloy, a metal oxide, a polyanionic compound. The anode may further corrode following the associated chemical reaction in discharge.

[0036] In a preferred embodiment, the anode comprises the metal or an alloy in its metallic form. An example of an alloy is that of magnesium and lithium. As will be described further below, the anode is preferably capable of contributing to or assisting in the in situ formation of a passivation layer which will serve as a separator between the anode and the cathode. Metals in their metallic forms and their alloys are considered to be reactive. In a lithium-ion battery it will be possible to use graphite, for example, lithiated graphite. In a sodium-ion battery it would be possible to use hard carbon as a component of the anode, for example, sodium hard carbon.

[0037] In one embodiment, the anode is selected from a metal plate and / or wafer, a compressed metal powder, and a metal powder-filled polymer. In one embodiment, the anode is a metal wire and / or strip.

[0038] In the context of this specification, the term in situ refers to a generation of the element concerned, generally the separator and / or the SEI, when the main elements, such as the anode and the cathode, have been assembled, put together and / or brought into contact, for example in a configuration which corresponds to that of the final battery. It is also possible to consider the element formed in situ as a solid electrolyte.

[0039] The method preferably comprises providing a cathode. In a preferred embodiment, the cathode is manufactured from a mixture of components comprising all the elements other than the anode necessary for the formation of the functional anode-separator-cathode assembly.

[0040] In one embodiment, the method of the invention comprises providing a mixture of components comprising a cathode active material and a reactive agent. Preferably, said mixture of components comprises at least one conductive material.

[0041] The active material of the cathode is a component that participates in the redox reaction where ionic species are reduced or oxidized, which allows obtaining a potential and an electric current to power a device. The active material can intercalate hydrogen ions and / or metal ions and / or anions or adsorb hydrogen ions and / or metal ions and / or anions or carry out a conversion reaction of this same material.

[0042] The active material of the cathode may comprise one or more of the following chemical elements: lithium, sodium, potassium, magnesium, calcium, manganese, zinc, iron, aluminum, copper, nickel, tin, vanadium, chromium, titanium, zirconium, molybdenum, lead, selenium, lanthanum, strontium, scandium, yttrium, cobalt, barium, niobium, ruthenium, phosphorus, palladium, platinum, tungsten, gold, silver, cadmium, tantalum, boron, carbon, nitrogen, oxygen, fluorine, chlorine, iodine, gallium, germanium, arsenic, indium, tin, antimony, iridium, bismuth, hydrogen, sulfur, silicon or alloys thereof.

[0043] The active material of the cathode may comprise one or more cations of one or more of the aforementioned metals, for example one or more metal cations such as, for example, one or more chosen from: Mg 2+ , Al 3+ , Zn 2+ Cu 2+ , Neither 2+ , Cr 3+ , Mn 2+ , Ag + , Fe 2+ , Fe 3+ , K+ , N / A + , In 3+ , Zr 2 , There 3+ , Nb 3+ .

[0044] In one embodiment, the cathode active material may be a metal salt, preferably a salt of a transition metal, preferably a salt of iron, manganese, chromium, nickel, cobalt, titanium, molybdenum, vanadium, zirconium, and tungsten. In one embodiment, the cathode active material comprises a halide, a phosphate, a sulfate, a nitrate, an organic anion, such as, for example, acetate, citrate, etc., of a transition metal, preferably one of the aforementioned metals.

[0045] In one embodiment, the cathode active material may be or comprise a metal oxide and / or one or more polyanionic compounds.

[0046] For example, the active material may be selected from: manganese oxide, manganese dioxide, iron oxide, chromium oxide, zinc oxide, magnesium oxide, aluminum oxide, nickel oxide, cobalt oxide, vanadium oxide, molybdenum oxide, dichromate, chromium trioxide, lead oxide, zinc oxide, titanium oxide, lithium oxide, sodium oxide, zirconium oxide, lanthanum oxide, silicon oxide, lead dioxide, iron oxychloride, bismuth oxychloride, vanadium oxychloride, chromium oxychloride, manganese oxychloride, titanium oxychloride, molybdenum oxychloride, cobalt oxychloride, zinc oxychloride, copper oxychloride, aluminum oxychloride, nickel oxychloride, lithium iron phosphate (LFP), spinel MmCk nickel manganese cobalt oxide (NMC), nickel cobalt aluminum oxide (NCA), sodium vanadium phosphate fluorine (NVPF), Prussian blue,sodium dichromate, sodium bismuthate, or oxygen (O2) or nitrogen or carbon dioxide. In one embodiment, the cathode active material may be or comprise a carbon-based active material whether electrically conductive or not such as: activated carbon, conductive porous carbon, graphite, graphene, graphene oxide and hard carbon, and mesocarbon microbeads (MCMB).,

[0047] In one embodiment, the active material of the cathode may be or comprise a porous material such as: a metal organic framework (MOF) or clay or organic polymer or porous conductive or non-conductive metal-organic polymer.

[0048] In one embodiment, the active material of the cathode may be or comprise a sulfur-based material such as: sulfur, iron sulfide, molybdenum sulfide, manganese sulfide, titanium sulfide, nickel sulfide, zinc sulfide or sulfur-rich polymer or any metal sulfide of the elemental material cited above in the section.

[0049] In one embodiment, the active material of the cathode may be or comprise an organic material such as the acid and / or the metal salt of the following compound: Benzoquinone; Ascorbate; Rhodizonate; 2,5-Dihydroxyterephthalic; 4-Hydroxyisophthalic 5-Ethynyl-1,3-benzenedicarboxyl; 5-Cyano-1,3; Benzenedicamyl; Phthalic Tetrachlorophthalic Anhydride; Tetrafluorotephthalic Diisodecyl Phthalate; 4-Hydroxyisophthalic 2,5-Dihydroxyterephthalic; 3-Fluorophthalic; Terephthalic; 2-Bromoterephthalic; 2-Hydroxyterephthalic Monoethyl Phthalate; Salicylic Mono-Cyclohexyl Phthalate; Tetrafluorophthalic Diisopropyl Phthalate; Dihexyl Phthalate; Ditricyclophthalic Phthalate; Diethyl phthalate; Dibutyl phthalate; Dimethyl terephthalate; Dimethyl 4-aminophthalic isophthalate; Isophthalic; Dimethyl 2-nitroterephthalic phthalate; Tetracyanoquino trimesic

[0050] In one embodiment, the cathode mixture of components comprises several different, for example two or more different, active materials. Preferably, a first active material is a conductive carbon (which also or mainly fulfills the function of conductive material) and a second active material comprises one of the aforementioned metals and cations as a component of the active material, for example selected from oxides, oxohalides (oxychlorides), phosphates, and / or sulfates, of the aforementioned metals and from polyanionic compounds as active materials. The reactive agent (hereinafter) which was not used during the formation of the SEI may in some cases also function as an active material.

[0051] The mixture of components for the preparation of the cathode preferably comprises a reactive agent.

[0052] A wide variety of materials can be used as a reactive agent.

[0053] In one embodiment, the reactive agent will function as an oxidizing agent. The reactive agent is an agent (or comprises an agent) that is capable of reacting preferentially with the anode and / or the cathode to contribute to the generation of an SEI ("Solid Electrolyte Interphase"). The SEI is a passivation layer, preferably formed in situ, that will function as a separator between the anode and the cathode. The formation of the SEI and thus the separator is described further below. The separator functions as an insulator, while allowing ions to diffuse between the anode and the cathode during operation of the battery.

[0054] In one embodiment, the reactive agent comprises an inorganic metal and / or acid salt and / or an organic metal and / or acid salt such as the family of halogens, sulfates, nitrates, persulfates, peroxides, trifluoromethanosulfonates, hexafluorophosphates, carboxylic, aromatic, citrates, acetates, permanganates, carbonates.

[0055] In a preferred embodiment, the reactive agent comprises or consists of a metal halide or metal oxohalide salt, preferably a metal chloride, fluoride, oxychloride or oxyfluoride salt. Preferably, the metal component of the salt of the reactive agent is selected from: sodium, lithium, magnesium, copper, zinc, calcium, manganese, zirconium, lanthanum, aluminum, iron, molybdenum, lead, cobalt, vanadium, chromium, nickel, silver, germanium, niobium, indium, selenium, scandium, tin, tungsten, and strontium. Preferably, the reactive agent comprises a chloride salt of one or more of the aforementioned metals.

[0056] For example, the reactive agent can be chosen from one or more of NaCl, LiCl, MgCh, KC1, CuCh, ZnCh, CaCh, MnCh, LaCh, AlCh, FeCh, FeCh, MOC16, MoCh, M02CI10, SnCh, SnCl4, C0CI2, VCh, VCI3, VCI4, VC15, CrCl3, NiCh, ZrCl3, ZrCl4, AgCl, GeCl2, GeCl4, NbCl3, NbCl4, NbCh, WC16, SrCh, NaF, LiF, MgF2, KF, CuF2, ZnF2, CaF2, MnF2, LaF3, A1F3, FeF2, FeF3, MoF6, M0F5, M02F10, SnF2, SnF4, C0F2, VF2, VF3, VF4, VF5, CrF3, CrF3, N1F2, ZrF3, ZrF4, AgF, GeF2, GeF4, NbF3, NbF4, NbF5, WF6, SrF2, FeOCl, VOC1, VO2C1, MnOCh, MnO2Cl2, MnO3Cl, ZrOCh.

[0057] In a preferred embodiment, the reactive agent is selected from NaCl, LiCl, MgCl2, KCl, CuCl2, CaCl2, FeCl3, AlCl3, MnCl2, Mode, ZrOCl2 and combinations comprising two or more of the above.

[0058] In one embodiment, the reactive agent comprises a metal cation such as one or more selected from: Mg 2+ , Cu 2+ , Neither 2+ , Cr 2+ , Cr 3+ , Mn 2+, Ag + , Fe 2+ , Fe 3+ and K + , N / A + , In + , Zr 2+ , There 3+ , Nb 3+ . In one embodiment, the reactive agent may be gaseous such as: dioxygen, dinitrogen, ozone, carbon dioxide, dichlorine, sulfur dioxide.

[0059] Preferably, the reactive agent, or at least one of its constituents, is capable of reacting with the anode, preferably a metal anode to form the SEI. Preferably, the reactive agent and the anode material are chosen in relation to each other, so as to allow the generation, preferably in situ, of an SEI.

[0060] In one embodiment, the reactive agent comprises a halide anion that contributes to the formation of the SEI and may also participate in the redox reaction as a cathode active material.

[0061] It is envisaged that not all of the reactive agent is consumed during the in situ formation of the SEI and that the remainder of the reactive agent that has not been consumed is a source of halide anions, e.g., chloride, in the case of anion battery operation, i.e., in the case where the anion is the redox species that migrates between the cathode and the anode.

[0062] In one embodiment, the reactive agent contains the cation of a metal present in the anode, preferably of the same metal as the anode if the latter comprises the metal in its metallic form.

[0063] In one embodiment, the anode comprises a metal in metallic form, and the reactive agent is a salt preferably comprising the same metal in cationic form. Preferably, the salt comprises a halide, oxohalide, preferably chloride or oxychloride, as mentioned above. For example, in an anode comprising magnesium metal, the reactive agent preferably comprises a magnesium cation. In another embodiment, the anode is metallized using the metal present in the reactive agent. For example, the anode comprises metallized graphite, for example, lithiated graphite, and the reactive agent comprises lithium ions. In another example, the anode comprises sodium hard carbon, and the reactive agent comprises sodium ions.

[0064] In a preferred embodiment, the mixture of cathode components comprises at least one electrically conductive material. When the active material used already has conductive properties, a separate conductor is not necessary. Similarly, if the binder (described in more detail below) is present and is conductive, a separate conductor is not required.

[0065] Generally, it can be said that the cathode mixture of components preferably comprises, in addition to the reactive agent, (i) a cathode active material, (ii) an electrical conductor and (iii) a binder, and the functions (i)-(iii) can be performed, in the cathode mixture of components, by one, two or three or even more different materials and / or compounds.

[0066] In a preferred embodiment, the conductive material comprises conductive carbon. The conductive carbon is preferably a carbonaceous material that is used to increase the electronic conductivity of the electrodes. Preferably, the conductive carbon is selected from super P carbon (SP carbon), graphite, graphene, graphene oxide, MCMB carbon, conductive organic carbon, conductive porous carbon, and combinations comprising two or more of the above materials.

[0067] According to a preferred embodiment, the active material already has conductive properties, and the active material thus also functions as a conductive material. In one embodiment, said cathode active material and said conductive material are the same material, preferably a carbon-based material.

[0068] The conductive carbon content may be reduced according to the preference of the skilled person to deliberately decrease the electronic conductivity of the cathode to achieve better performance. For example, a less reactive metal such as zinc or manganese may be combined with a less conductive component mixture to force the direction of current flow from the anode to the cathode.

[0069] In one embodiment, the conductive material comprises a conductive polymer, preferably a conductive organic polymer, i.e. polymers that can have electrical conductivity, in particular the movement of electrons (and not by diffusion of ions). Examples of conductive polymers are: melanin, polypyrroles, polyanilines, polycarbazoles, polyindoles, polyazepines, polythiophenes (PT), poly(p-phenylene sulfide) (PPS), polyacetylenes, poly(p-phenylene vinylene) (PPV), polyfluorenes, polypyrenes, polyazulenes, polynaphthalenes. Some of these polymers are preferably doped in order to obtain the desired conductive properties.

[0070] In one embodiment, the conductive material and the cathode active material are constituted by a single material or by two different materials, and the binder is preferably different from the conductive material and the cathode active material. In other words, according to this embodiment, the binder functions essentially as a binder and not as a cathode active material or as a conductive material.

[0071] According to one embodiment, the active cathode material and the current conductor are potentially present in the form of a single material, preferably in the form of a conductive carbon having the property of active insertion and / or adsorption and / or catalysis material.

[0072] In a preferred embodiment, the functional battery comprises a cation capable of migrating between the anode and the cathode during discharge of the battery and / or an anion capable of migrating between the cathode and the anode during discharge of the battery.

[0073] The cation is preferably likely to migrate towards the cathode and then be reduced after being oxidized at the anode during battery discharge.

[0074] The anion is preferably likely to migrate towards the anode and then reduced after being oxidized at the cathode during battery discharge.

[0075] In a preferred embodiment, the cation is generally a metal cation, for example selected from the cations of magnesium, iron, manganese, zinc, aluminum, lithium, sodium, potassium, calcium, manganese, titanium and a combination of two or more of the above. The cation may be selected from the cations of the reactive agent. Preferably, the cation is added to the mixture of components of the cathode as a reactive agent, as a cathode active material and / or as an ionic additive, so that it does not need to be added separately. In a preferred embodiment, the cation is released from the anode, for example when the anode is formed from a metal in its elemental form and / or if the anode comprises the metal.

[0076] In a preferred embodiment, the cation is added as a cationic element of the reactive agent. Preferably, the released metal cation is the metal cation of the reactive agent.

[0077] In a preferred embodiment, one, several or all selected from said active material, said reactive agent, said anode, and, if present, said ionic additive is capable of releasing at least one metal cation preferably selected from cations of magnesium, iron, lithium, sodium, potassium, calcium, manganese, indium, zinc, aluminum, lead, titanium, zirconium, lanthanum, cobalt, nickel, molybdenum, copper and a combination of two or more of the above. For example, a metal cation present in the reactive agent may be released.

[0078] In a preferred embodiment, one, several or all selected from said active material, said reactive agent, said anode, and, if present, said ionic additive is capable of releasing at least one anion. The anion may be inorganic and / or organic. In one embodiment, the anion is preferably selected from halides such as fluoride, chloride, iodide, bromide and a combination of two or more of the above, and also from CCL anions 2 ' , NCS', CN', NCO'. Preferably, the flag is chosen from halides, in particular from chloride and / or fluoride. More preferably, the flag is a chloride flag.

[0079] In a preferred embodiment, flag is flag present in the salt of the reactive agent and / or in the cathode active material.

[0080] In a preferred embodiment, said mixture of components comprises a binder, preferably chosen from polymers.

[0081] The binder is preferably a material that holds together and agglomerates said active material, said reactive agent, said conductive material if the latter is separately added, and said ionic additive if present. The binder preferably facilitates assembly of the battery in a roll-to-roll process and allows for better adhesion between the anode and the cathode when creating the SEI. In one embodiment, the binder may be a biodegradable or synthetic polymer. The binder may also be a natural polymer.The binder may comprise, for example, one or more of: cellulose, alkylated, acetylated, carboxylated and / or carboxyalkylated cellulose, for example a carboxyalkylcellulose, for example carboxymethylcellulose, cellulose acetate, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene oxide, polypropylene oxide, polyphenylene sulfide, polyphenylene oxide, polyethylene, polyether ether ketone, polyphthalamide, polypyrrole, polyaniline, polysulfone, xydar, polyacrylonitrile, dextrin.

[0082] In one embodiment, the binder is capable of promoting ionic conduction whether it is anionic or cationic, preferably anionic, such as glycol ethers.

[0083] In one embodiment, said mixture of components further comprises an ionic additive. The ionic additive is preferably added to the cathode mixture of components, preferably in the form of a salt. Said ionic additive preferably comprises an anion and / or a cation contributing to the mobility of the ions, for example, within the cathode and / or the entire anode.

[0084] Preferably, the ionic additive increases the energy density as well as the power of the battery.

[0085] It should be noted that the ionic additive and the reactive agent are preferably added in the form of a salt. The reactive agent is a mandatory constituent of the cathode mixture of components and the ionic additive is optional. If the ionic additive is present, it is a different material or additive than the reactive agent. Then, the reactive agent and, if present, the ionic additive, are preferably different materials from the cathode active material and the conductive material.

[0086] This is different from the conductive material situation described above, which may consist of the cathode active material, if the latter material is conductive, or the binder, if the binder is conductive. The conductive material and the cathode active material may be the same single material. Similarly, the binder and / or the conductive material could be the same material. Finally, it would be possible for the active material, the conductive material, and the binder to be present as a single material.

[0087] In one embodiment, the ionic additive provides improved diffusion of ions (anions and / or cations) within the cathode and / or the anode. The ionic additive may be a monovalent, divalent, or trivalent solid ionic conductor that may be polymer-based, sulfide-based, oxide-based, ceramic-based, or halide-based, such as: a mixture of polyethylene oxide (PEO) and LiTFSI salt, lithium indium chloride (Li3InC16), lithium thiophosphate (Li2S-P2S), LiOGeP2S12 (LGPS), and Li7La3Zr20i2 (LLZO).

[0088] The ionic additive can be a solid ionic conductor conducting anions which can be based on polymer as mentioned above, metal hydroxide such as the compounds called LDH for "layered double hydroxide".

[0089] In one embodiment, the ionic additive, when present, comprises at least one anion from the halogen family.

[0090] In one embodiment, the ionic additive, when present, comprises at least one metal cation, preferably of the same metal capable of being released from the cathodic mixture of components, preferably the same cation present in the reactive agent. According to a preferred embodiment, the anode comprises in its elemental form said cation.

[0091] In one embodiment, providing a mixture of components comprises adding a solvent. The purpose of the solvent is to facilitate mixing and / or to generate a paste that assists in shaping the cathode. Preferably, the dry components and the solvent are mixed until a homogeneous paste is obtained. For example, the components of the mixture of cathode components may be formed into a paste, which may be directly applied to the anode, or which may be deposited as a film, or in a void form, to obtain the cathode following evaporation of the solvent. The cathode may be cut, for example by cutting the deposited film or the form following drying.

[0092] The solvent is preferably selected from water and volatile organic solvents. The solvent may be polar or non-polar and may be protic or aprotic. Preferably, a polar solvent is used. For example, the solvent is selected from water, ethanol, acetone and acetonitrile.

[0093] It should be noted that the cathode can also be formed without the use of a solvent. For example, the mixture of cathode components can be compressed to form a desired shape, such as a pellet, which is then used directly as the cathode. In another example, the mixture of cathode components can be directly compressed with the anode in a final assembly mode.

[0094] Without wishing to be bound by theory, the present inventor of this invention believes that the operational chemistry of the battery is innovative. The present invention discloses a new battery chemistry concerning a cathode loaded with salts in dissolved and / or amorphous and / or micronized form in a solid which, associated in particular with a metal, create the battery according to the invention. It constitutes an embodiment that is extremely easy to industrialize.

[0095] As mentioned, the preparation of the cathode component mixture generally involves the addition of a salt, for example in the form of the reactive agent or, where appropriate, the ionic additive. In all cases, the battery will contain charged redox species, anions and / or cations, which may crystallize, especially in the absence of a liquid solvent and / or an electrolyte.

[0096] Preferably, one or more selected from the active material, the conductive material, the ionic additive and / or the binder are chosen so as to prevent crystallization of the added salt(s), in particular when the solvent is evaporated. These components are preferably chosen so as to allow and / or facilitate the dissolution of the salts in a dry medium free of solvent, for example of the reactive agent, and / or to promote the amorphous, complexed and / or dissolved form of the salt in a dry medium free of solvent. In this way, a liquid electrolyte is preferably absent, because the components of the anode allow the ions to migrate into the matrix formed by the cathode. The presence of the ions in the cathode mixture of components is due to the choice of the components, for example of the active material, the reactive agent, the conductive agent and / or the binder.One, several, or preferably all of these components are chosen to favor the ionic or amorphous, non-crystalline form of the salts, even if a solvent is not used or when the solvent is evaporated.

[0097] In one embodiment, the reactive agent is dispersed in the active material or binder or conductive material or combination of two or three of the above components so that no solvent is required.

[0098] In a preferred embodiment, said active cathode material, said conductive material and, where appropriate, said binder, are chosen so as to allow the presence in amorphous form, in complexed form and / or in dispersed form of the salts added to the mixture of components, in particular of the reactive agent.

[0099] Preferably, one or more chosen from the active material, the conductive material and / or the binder are porous and / or the cathode obtained with one or more of these components is porous and makes it possible to absorb and / or complex the atoms or molecules in their anionic, cationic and / or micronized form.

[0100] In one embodiment, the method comprises preparing the cathode. The cathode is prepared from the cathode mixture of components. Preferably, these components include an active material and a reactive agent. Preferably, a binder is also added to form the mixture. If neither the active material nor the binder is conductive, a material having electrical conduction properties is added separately. Some active materials have conductive properties. In this case, a separate conductor is not necessary.

[0101] Other components, for example an ionic additive, can be added to the component mixture

[0102] Preferably, these components of the cathode mixture of components are added in the form of powders.

[0103] In a preferred embodiment, the active material, the conductive material and / or the binder are capable of adsorbing and / or complexing salts, molecules, etc., in ionic or micronized form. This applies in particular to the reactive agent, which is preferably added in the form of a salt, preferably a metal halide.

[0104] The cathode is preferably prepared by adding a solvent to mix and, if necessary, help dissolve the components, to form a homogeneous paste. The homogeneous paste can then be deposited and dried. Due to the above, the presence of the solvent in the cathode mixture of components is in principle optional.

[0105] In a preferred embodiment, the method comprises forming a cathode by compressing said mixture of components, preferably using a sufficiently high pressure and temperature and / or a temperature chosen to assume a defined, condensed and / or solid shape, preferably during final assembly of the battery i.e. compressed directly with the anode.

[0106] In one embodiment, said cathode active material and said reactive agent are different materials which are preferably mixed and / or ground before being added and / or mixed with said conductive material and / or binder. The invention contemplates heating the reactive agent and the cathode active material, for example to 100°C or more. Before contacting for the formation of the SEI according to the method of the invention, the cathode mixture of components is preferably cooled to correspond to the temperatures mentioned below.

[0107] The mixing / grinding of the cathode active material and the reactive agent corresponds to a premix and is preferably applied when said cathode active material is or comprises a metal oxide and / or oxohalide. Preferably, according to this embodiment, the separately prepared premix is ​​then mixed with said conductive material and / or the binder, it being understood that said conductive material may also comprise a(nother) active material, such as conductive carbon-based active materials, for example.

[0108] In a preferred embodiment, the method comprises inducing the in situ formation of a passivation layer. Preferably, this step comprises contacting the mixture of components with the anode.

[0109] An advantage of the invention is that the components of the cathode mixture can be used at room temperature and / or the contacting of the mixture of components with the anode can take place at room temperature, for example at a temperature of 10 to 40°C, preferably 15 to 30°C, more preferably 18 to 25°C.

[0110] More generally, it is not necessary to heat and / or melt components of the cathode mixture before bringing the cathode mixture of components into contact with the anode, and the invention preferably does not include and / or preferably excludes the heating and / or melting of polymers, in particular organic polymers, for example conductive polymers.

[0111] In a preferred embodiment, the components of the cathode mixture, the mixture and / or the anode, preferably have a temperature below 200°, preferably below 150°C, preferably below 100°C, more preferably below 80°C, 70°C, 60°C, 50°C, and 40°C, when the cathode mixture and the anode are brought into contact. The temperature is preferably chosen so that the solvent, if present, is present in a liquid form. The invention does not exclude that even lower temperatures are chosen. For example, it is possible that the contacting can be carried out from a temperature of -10°C, from -5°C, from 0°C, from 5°C, and preferably from °10C.

[0112] In one example, a cathode is formed from the mixture of components, and the formed cathode is then brought into contact with the anode. In the case where a paste has been formed by adding a solvent to the dry components of the cathode mixture of components, it is possible to dry the mixture in order to obtain the final cathode. The latter is brought into contact with the anode

[0113] According to another example, the mixture of components comprising the solvent, for example the above-mentioned paste, is directly contacted with the anode. In this case, the solvent is preferably evaporated and / or dried after the assembly of the anode and the cathode, which is also covered by the present invention.

[0114] In one embodiment, said mixture of components is a paste comprising a solvent, said paste being contacted with said anode, or said paste being dried prior to contacting the dried component mixture with said anode.

[0115] As the person skilled in the art knows, certain components, such as lithium metal or lithium salts, are reactive in the presence of air and / or moisture, which is why the manufacture of the cathode and the assembly of the battery must be carried out in a protected environment or inert atmosphere, such as an atmosphere deprived of oxygen, nitrogen and moisture, for example in a chamber under an inert gas such as argon or in a chamber deprived of moisture in the air.

[0116] Surprisingly, bringing the cathode prepared as described into contact with the anode results in the in situ creation of a passivation layer functioning both as a separator and as a solid electrolyte.

[0117] While this passivation layer forms spontaneously, the invention does not prevent the separate preparation of a film having a composition similar to the passivation layer and the assembly of the battery by placing the film between the anode and the cathode. In this case, a functional battery can also be obtained. It would also be possible to use a separator having a composition other than that of the spontaneously formed passivation layer. In principle, the separate creation of the separator and the assembly using the separate separator constitutes an additional step and is not considered advantageous according to the invention, since this step is not mandatory.From another perspective, this separate step could be considered advantageous, even if it involves one or more additional steps, when they allow the constitution and / or the dimension of the separator to be better defined or when they allow the avoidance of a chemical reaction which cannot be controlled.

[0118] In some embodiments, the battery of the invention may be manufactured without a current collector and / or may lack a current collector. In one embodiment, the battery lacks an anode current collector. In one embodiment, the battery lacks a cathode current collector. In one embodiment, the battery lacks both current collectors. The anode and / or the cathode may directly function as the current collector in these cases.

[0119] Figure 1A shows an anode 11 and a cathode 12 before contacting. Figure 1B shows a battery 1 without a current collector. Battery 1 has an anode 11, a cathode 12, and the separator 13. Figure 1C shows a battery 2 having an anode current collector 21 in addition to the aforementioned components. Figure 1D shows a battery 3 having an anode current collector and a cathode current collector 22.

[0120] A configuration with one or no current collector is conceivable due to the possible high conductivity of the anode and the cathode. As described above, the anode can be made in the form of a metal, for example a wire or a metal plate, which is why a separate current collector is not necessary in all cases. On the cathode side, it necessarily contains a conductive material, which is why a cathode current collector may be absent. In addition to the possibility of using non-toxic and biodegradable materials, the battery is preferably in the solid state and therefore without electrolyte, which allows the battery to be manufactured without packaging and without an additional current collector, furthermore the current collectors can be provided by the manufacturer of devices capable of accommodating a battery from among the present invention.Figure 2 shows a battery 4 having a wire functioning as an anode 31 and the cathode 32 being deposited on a portion of the anode. The separator 33 formed in situ is indicated in Figure 2, whereas it would not be visible from the outside, because it is covered by the cathode and present between the anode and the cathode in order to prevent a short circuit.

[0121] In conventional battery configurations, current collectors are present in the overall construction, and the invention will thus generally be implemented with current collectors. Similarly, when one of the components must be protected, such as lithium, a casing, covering or protection is required.

[0122] Figure 3 shows a battery 5 in the form of a button cell, comprising an anode 51, a cathode 52, anode and cathode current collectors 61 and 62, respectively, a sealing ring 230, a spring 55 and a positive case or protection 65. The in-situ formed separator 13 is also present. The anode current collector also functions as a negative case or protection (on the anode side).

[0123] When a current collector is present (or both), it may be selected from metals, conductive (organic) polymers, carbon fibers, and conductive carbon-filled polymers. For example, the conductor may be selected from aluminum, copper, stainless steel, zinc, iron, stainless steel, graphite, graphene, polyvinylpyrrolidone, and polyaniline.

[0124] The current collector generally does not participate in redox reactions, if there is redox activity in the current collectors during charging or discharging.

[0125] However, in embodiments in which protection of the components is not necessary, for example in the case of a magnesium battery, the possibility of omitting the current collector also implies a great deal of freedom in terms of the shape and dimensions of the battery according to the invention. Due to the absence of a housing, cladding or / or protection, the battery can be created with any shape and the shape can thus be adapted to a particular need and / or situation, or even to any situation.

[0126] As described above with respect to the preparation of the cathode from a mixture of components, it is easily possible to give any desired shape to the cathode, whether by compression, for example in the absence of a solvent, or by the formation of a malleable and deformable paste in the presence of a solvent.

[0127] A surprising and advantageous aspect of the present invention is the provision of a generalized approach and / or framework for preparing primary and / or secondary batteries preferably without liquid electrolyte from a large number of components and following a generalized manufacturing method. The invention implements a very simple and generalized method for manufacturing a battery whose characteristics and / or battery type can be chosen according to the need, for example according to the desired electrical potential. The concept of the invention allows adaptation to secondary batteries.

[0128] In one embodiment, the invention relates to a battery obtained according to the manufacturing method disclosed in the present description.

[0129] In one embodiment, the invention relates to a battery without liquid electrolyte and / or a solid-state battery comprising a cathode, an anode, a separator of the solid-electrolyte interface (SEI) type.

[0130] In one embodiment, the battery comprises a separator and / or solid electrolyte formed in situ, following the assembly of the initial constituents of the battery, preferably between the anode and the cathode.

[0131] In one embodiment, the invention provides a battery in which the cathode comprises conductive carbon. In another embodiment, the mixture of components is free of conductive carbon and comprises a cathode active material other than conductive carbon.

[0132] In one embodiment, the invention relates to a battery in which said anode comprises one or more selected from a metal in its metallic form, graphite, hard carbon, activated carbon, a metal alloy, a metal oxide, a polyanionic compound and a combination of several of the aforementioned materials. In one embodiment the anode comprises or consists of a metal layer.

[0133] In one embodiment, the battery of the invention is devoid of an electrolyte, preferably a liquid electrolyte and / or an added solid electrolyte. The separator is preferably formed in situ and can also be considered a solid electrolyte. The in situ formed material can be considered to constitute said separator and / or a solid electrolyte. An added solid electrolyte, in addition to the separator and / or the mentioned in situ formed material, is preferably absent. In particular, a solid and / or liquid electrolyte added separately and / or added as a constituent element of the battery is absent. A separator added separately and / or added as a constituent element of the battery is preferably also absent.

[0134] In one embodiment, the battery of the invention comprises a separator (or solid electrolyte) formed in situ, following the assembly of the initial constituents of the battery, preferably between the anode and the cathode. In one embodiment, said separator comprises one or more chosen from a metal oxide, a metal hydroxide and a metal salt, preferably chosen from an oxide, oxohalide, hydroxide and / or salt of the redox species and / or an oxide, oxohalide, hydroxide and / or salt of the anode metal.

[0135] In one embodiment, the cathode of the battery of the invention comprises an element selected from magnesium, iron, lithium, sodium, potassium, calcium, manganese, zinc, aluminum, lead, titanium, zirconium, lanthanum, cobalt, nickel, molybdenum, copper, chromium, oxygen, sulfur and a combination comprising two or more of the aforementioned metals, preferably in ionic form, such as cationic and anionic where appropriate.

[0136] In one embodiment, the anode of the battery of the invention comprises an element selected from magnesium, iron, lithium, sodium, potassium, calcium, manganese, zinc, aluminum, lead, titanium, zirconium, lanthanum, cobalt, nickel, molybdenum, copper, chromium, and a combination comprising two or more of the aforementioned metals. The element is preferably present in its metallic form, and / or said element is the same element (e.g. a metal) as the cation present in the cathode.

[0137] In one embodiment, the battery of the invention is rechargeable and / or intended for single use and / or discharge.

[0138] In one embodiment, the battery of the invention is biodegradable.

[0139] In one embodiment, anion, in particular an anion selected from halides, is the redox species that migrates in ion form between the anode and the cathode. In one embodiment, the battery is of the halide ion type, ("chloride-, fluoride-, iodide-, or bromide-ion"). Those skilled in the art will not encounter any particular difficulty in adapting the content of the present disclosure to their own needs and implementing a battery, primary or secondary, without departing from the scope of the present invention.

[0140] Examples:

[0141] Example 1: Primary magnesium battery without fully biodegradable electrolyte and without current collector

[0142] This example involves the manufacture of a solid-state, fully biodegradable battery to power, preferably, a device that consumes microwatts of power.

[0143] This primary battery is composed only of biodegradable materials such as magnesium metal which is biocompatible and biodegradable, and which slowly dissolves into magnesium hydroxide and then into Mg 2+ and H2O due to the pH of the soil. Porous charcoal is a non-toxic and edible material used in medicines. Also used are cellulose, which is indeed biodegradable, and magnesium chloride, which is also edible and used in food.

[0144] Composition of the anode:

[0145] The anode is made of magnesium metal, here we use magnesium wire.

[0146] Composition of the cathode:

[0147] The cathode is formed from an active material, a reactive agent and a binder as follows:

[0148] 1. Porous conductive vegetable carbon 50% (by weight) used as both cathode active material and conductive material,

[0149] 2. Magnesium chloride (MgCh) 40% as a reactive agent,

[0150] 3. Cellulose powder 10% (commercially available as papier-mâché) as a binder.

[0151] Preparation of the cathode component mixture:

[0152] Porous conductive vegetable carbon, magnesium chloride and cellulose powder are mixed with a small amount of water as a solvent in a cup until a homogeneous black paste is obtained. Battery assembly:

[0153] The resulting homogeneous black paste is applied around the magnesium wire so that part of the magnesium wire remains free to obtain electrical contact with the anode. This assembly is left to dry in the presence of ambient air and at room temperature (in the presence of oxygen in the air) so that the water evaporates and the paste becomes solid.

[0154] It should be noted that this battery is functional without a current collector being added to either the cathode or anode side, both electrodes can be used directly as current collectors.

[0155] The battery is biodegradable, as mentioned above.

[0156] In this example, the battery has a wire format, but it can be produced in any desired shape.

[0157] For example, this battery can be used to power small electronic devices and / or low-power devices such as watches, thermometers, pregnancy tests, toys, and / or sensors.

[0158] The battery is shown in Figure 2.

[0159] Example 2: Fully biodegradable primary battery without magnesium electrolyte and without current collector using PVP as polymer

[0160] This example involves the manufacture of a completely solid-state, fully biodegradable battery to power a low-power device.

[0161] This primary battery is made up of only biodegradable materials like magnesium metal which is biocompatible and biodegradable. Graphite which is a non-toxic material used, polyvinylpyrrolidone (PVP) is a biodegradable and biocompatible polymer and sodium chloride is also edible and used in food.

[0162] Anode composition: For the anode magnesium wire is used as in example 1.

[0163] Composition of the cathode:

[0164] The cathode is formed from an active material, a reactive agent and a binder as follows:

[0165] 1. Graphite 40% as active material,

[0166] 2. sodium chloride (NaCl) 30% as a reactive agent,

[0167] 3. polyvinylpyrrolidone (PVP) 10% as binder.

[0168] Preparation of the cathode component mixture:

[0169] Graphite, sodium chloride, polyvinylpyrrolidone powder and a small amount of water as solvent are mixed in a beaker until a homogeneous viscous liquid is obtained.

[0170] Battery assembly:

[0171] The battery is assembled as described for the previous examples, applying the homogeneous viscous liquid around the magnesium wire. Figure 2 shows the battery schematically.

[0172] Example 3: Primary battery without fully biodegradable magnesium electrolyte and without current collector using carboxymethyl cellulose as polymer

[0173] This example involves the manufacture of a completely solid-state, fully biodegradable battery to power a low-power device.

[0174] This primary battery is made up of only biodegradable materials like magnesium metal which is biocompatible and biodegradable. Graphite which is a non-toxic material used, polyvinylpyrrolidone (PVP) is a biodegradable and biocompatible polymer and sodium chloride is also edible and used in food.

[0175] Composition of the anode:

[0176] For the anode magnesium wire is used as in example 1.

[0177] Composition of the cathode:

[0178] The cathode is formed from an active material, a reactive agent and a binder as follows:

[0179] 4. 50% carbon black as active material,

[0180] 5. sodium chloride (NaCl) 40% as reactive agent, 6. carboxymethyl cellulose (CMC) 10% as binder.

[0181] Preparation of the cathode component mixture:

[0182] Carbon black, sodium chloride, carboxymethyl cellulose powder and a small amount of water as solvent are mixed in a beaker until a homogeneous viscous liquid is obtained.

[0183] Battery assembly:

[0184] The battery is assembled as described for the previous examples, applying the homogeneous viscous liquid around the magnesium wire. Figure 2 shows the battery schematically.

[0185] Example 4: Primary battery of magnesium powder without fully biodegradable electrolyte and without current collector

[0186] This example involves the manufacture of a solid-state, fully biodegradable battery to power, preferably, a device that consumes microwatts of power.

[0187] Composition of the anode:

[0188] The anode is made of magnesium metal, here we use magnesium metal powder in a cellulose acetate polymer prepared in a solvent like acetone.

[0189] Cellulose acetate is dissolved in acetone and then magnesium powder is added. Once the solvent has evaporated, a polymer film loaded with metallic magnesium particles remains, which constitutes the anode.

[0190] Composition of the cathode:

[0191] The cathode is formed from an active material, a reactive agent and a binder as follows:

[0192] 4. Porous conductive vegetable carbon 50% (by weight) used as both cathode active material and conductive material,

[0193] 5. Magnesium chloride (MgCh) 40% as a reactive agent,

[0194] 6. Cellulose powder 10% (commercially available as papier-mâché) as a binder.

[0195] The mixing of components is carried out as described in Example 1. Battery assembly:

[0196] The resulting homogeneous black paste is applied around the magnesium wire so that part of the magnesium wire remains free to obtain electrical contact with the anode. This assembly is left to dry in the presence of ambient air and at room temperature (in the presence of oxygen in the air) so that the water evaporates and the paste becomes solid.

[0197] It should be noted that this battery is functional without a current collector being added to either the cathode or anode side, both electrodes can be used directly as current collectors.

[0198] The battery is biodegradable, as mentioned above.

[0199] In this example, the battery has a wire format, but it can be produced in any desired shape.

[0200] For example, this battery can be used to power small electronic devices and / or low-power devices such as watches, thermometers, pregnancy tests, toys, and / or sensors.

[0201] The battery is shown in Figure 2.

[0202] It is contemplated that the invention may be applied to other types of anodes and / or batteries. Hereinafter, contemplative examples 5 to 11 are extrapolations of the concept of the invention.

[0203] Example 5: Primary battery without high voltage magnesium electrolyte and without current collector

[0204] This example involves making a high-voltage, all-solid-state battery to power, preferably, a device that consumes microwatts of power.

[0205] Composition of the anode:

[0206] The anode is made of magnesium metal, here we use a magnesium strip

[0207] Composition of the cathode:

[0208] The cathode is formed of an active material, a reactive agent and a binder as follows: 1. 20% porous conductive vegetable carbon used as both the cathode active material and the conductive material,

[0209] 2. manganese dioxide (Mn02) 40% as active material

[0210] 3. iron chloride (FeCl3) 30% as a reactive agent,

[0211] 4. 10% cellulose powder as in example 1.

[0212] Preparation of the cathode component mixture:

[0213] Porous conductive vegetable carbon, iron chloride and manganese dioxide are premixed in a mortar and then added to cellulose powder dissolved in a small amount of water as a solvent in a cup until a homogeneous black paste is obtained.

[0214] Battery assembly:

[0215] The homogeneous black paste is applied all around the wire so that a part of the wire remains free to obtain the electrical contact of the anode. This assembly is left to dry in the presence of ambient air and at room temperature (in the presence of oxygen in the air) so that the water evaporates and the paste becomes solid.

[0216] The resulting battery corresponds to the diagram shown in Figure 2. It can be used in the same devices as those mentioned in Example 1.

[0217] Example 6: Primary battery without iron electrolyte and without current collector

[0218] This example involves the manufacture of a fully biodegradable, all-solid-state battery to power, preferably, a device that consumes microwatts of power.

[0219] Composition of the anode:

[0220] The anode is made of iron metal, here we use pure iron wire.

[0221] Composition of the cathode:

[0222] The cathode is formed from an active material, a reactive agent and a binder as follows:

[0223] 1. 60% porous conductive vegetable carbon used as both cathode active material and conductive material,

[0224] 2. iron chloride (FeCl3) 30% as a reactive agent,

[0225] 3. 10% cellulose powder as in example 1. Preparation of the cathode component mixture:

[0226] Porous conductive vegetable carbon, iron chloride and cellulose powder are mixed with a small amount of water as a solvent in a cup until a homogeneous black paste is obtained.

[0227] Battery assembly:

[0228] The homogeneous black paste is applied all around the wire so that a part of the wire remains free to obtain the electrical contact of the anode. This assembly is left to dry in the presence of ambient air and at room temperature (in the presence of oxygen in the air) so that the water evaporates and the paste becomes solid.

[0229] The resulting battery corresponds to the diagram shown in Figure 2. It can be used in the same devices as those mentioned in Example 1.

[0230] Example 7: Primary battery without lithium electrolyte

[0231] This example is for a lithium-ion battery to power a device that currently uses a lithium-ion battery.

[0232] Composition of the anode:

[0233] The anode is made of lithium metal.

[0234] Composition of the cathode:

[0235] The cathode comprises an active material, reactive agent and a binder as follows:

[0236] 1. 50% carbon black as active material,

[0237] 2. Lithium chloride (LiCl) 40% as reactive agent,

[0238] 3. Polyvinylidene fluoride (PVDF) 10% as binder.

[0239] Preparation of the cathode component mixture:

[0240] The above cathode components are mixed, under an inert atmosphere, deprived of oxygen and moisture, in a beaker with acetone as the solvent which dissolves the PVDF until a homogeneous black viscous liquid is obtained, then the liquid is poured onto a flat surface and allowed to dry slowly to form a uniform thin polymer film. Then, a disc is cut from the dried cathode mixture. Battery assembly:

[0241] In the absence of oxygen and moisture, the battery is assembled into a button cell with dimensions defined by the international standard. The empty battery has a negative part and a positive part between which the battery components will be assembled.

[0242] A lithium metal disc (anode) is added inside the negative part, then the cathode disc is placed directly in contact with the anode. Next, the current collector disc and a spring are placed on the cathode and the assembly is hermetically sealed using the positive part of the standard button cell. Finally, the button cell is crimped using a crimping tool which will permanently seal the battery and make it airtight and waterproof.

[0243] Figure 3 shows a schematic of this lithium battery.

[0244] This battery can power low power and high power devices like watches, thermometers, pregnancy tests, toys, sensors, LEDs, controllers, smartphone, electric vehicle and by extension all devices that use at least a 3V primary or rechargeable battery.

[0245] Example 8: Primary battery without sodium electrolyte

[0246] This example concerns the manufacture of an electrolyte-free sodium-ion battery to power a device that currently uses a lithium-ion battery.

[0247] Composition of the anode:

[0248] The anode is made of sodium metal.

[0249] Composition of the cathode:

[0250] The cathode is composed of an active material, a reactive agent and a binder which are:

[0251] 1. Carbon black 50% as active material,

[0252] 2. Sodium chloride (NaCl) 20% as a reactive agent,

[0253] 3. Polyvinylidene fluoride (PVDF) 30% as binder.

[0254] The preparation of the cathode component mixture and the assembly of the button cell type battery are as described in Example 5. Example 9: Primary battery without calcium electrolyte

[0255] This example concerns the manufacture of an electrolyte-free calcium-ion battery to power a device that currently uses a lithium-ion battery.

[0256] Composition of the anode:

[0257] The anode is made of calcium metal.

[0258] Composition of the cathode:

[0259] The cathode is composed of an active material, a reactive agent and a binder which are:

[0260] 1. Carbon black 50% as active material,

[0261] 2. Calcium chloride (CaCl) 40% as a reactive agent,

[0262] 3. Polyvinylidene fluoride (PVDF) 10% as binder.

[0263] The preparation of the cathode component mixture and the assembly of the button cell type battery are as described above in Example 4.

[0264] Example 10: Secondary battery without lithium electrolyte

[0265] This example is for an electrolyte-free lithium-ion battery to power a device that currently uses a lithium-ion battery. The battery can be rechargeable.

[0266] Composition of the anode:

[0267] The anode is made of lithium metal.

[0268] Composition of the cathode:

[0269] The cathode is composed of an active material, a reactive agent and a binder which are:

[0270] 1. Lithium iron phosphate (LFP) 80% as active material,

[0271] 2. lithium chloride (LiCl) 10% as reactive agent,

[0272] 3. Polyvinylidene fluoride (PVDF) 10% as binder.

[0273] Example 11: Secondary battery without lithium electrolyte

[0274] This example is for an electrolyte-free lithium-ion battery to power a device that currently uses a lithium-ion battery. The battery can be rechargeable.

[0275] Anode composition: The anode is composed of lithium metal.

[0276] Composition of the cathode:

[0277] The cathode is composed of an active material, a reactive agent and a binder which are: 1. Manganese dioxide (MnCL) 80% as active material,

[0278] 2. carbon SP 10% as conductive agent,

[0279] 3. lithium chloride (LiCl) 10% as a reactive agent,

[0280] 4. Polyvinylidene fluoride (PVDF) 10% as binder. The preparation of the cathode and the assembly of the battery into a button cell are carried out according to the steps described in Example 7.

Claims

Claims 1. A method for manufacturing a liquid electrolyteless battery and / or a solid state battery, the method comprising: providing a cathodic mixture of components comprising a cathode active material and a reactive agent, said mixture of components preferably providing at least the constituents of a cathode, and said mixture of components comprising at least one conductive material; providing an anode; inducing the in situ formation of a passivation layer by contacting the cathodic mixture of components with the anode, said passivation layer functioning as a separator between the anode and the cathode.

2. The method according to claim 1, characterized in that said mixture of components comprises a metal cation and an anion, said cation and / or said anion being added in the form of a salt to the cathodic mixture of components, and said cation and / or said anion being capable of being released from the cathodic mixture of components.

3. The method according to claim 2, characterized in that said anion is a halide anion, preferably chosen from chloride, fluoride, iodide, bromide, preferably chloride.

4. The method according to any one of the preceding claims, characterized in that one, several or all chosen from said active material, said reactive agent, said anode, and, where appropriate, an ionic additive, is capable of releasing a metal cation chosen from the cations of magnesium, iron, lithium, sodium, potassium, calcium, manganese, indium, zinc, aluminum, lead, titanium, zirconium, lanthanum, cobalt, nickel, molybdenum, copper, chromium, tungsten and a combination of two or more of the above.

5. The method according to any one of the preceding claims, characterized in that said reactive agent, or at least one of its constituents, is capable of reacting with said anode and of contributing to the generation of said passivation layer between the anode and the cathode.

6. The method according to any one of the preceding claims, characterized in that said conductive material comprises one or more chosen from conductive carbon and conductive organic polymers.

7. The method according to any one of the preceding claims, said reactive agent being chosen from halogen and oxohalide metal salts, preferably chloride, fluoride, oxychloride and oxyfluoride metal salts.

8. The method according to claim 7, said reactive agent being chosen from halogen metal salts preferably comprising the metal cation according to claim 4.

9. The method according to any one of the preceding claims, in which said active material of the cathode comprises a material chosen from an electrically conductive or non-conductive carbon, vegetable charcoal, graphite, carbon black, a metal oxide, a metal phosphate, a polyanionic compound, a halide, an organic molecule.

10. The method according to any one of the preceding claims, characterized in that the anode comprises magnesium, preferably magnesium metal.

11. The method according to any one of the preceding claims, characterized in that the anode comprises one or more chosen from iron, zinc, aluminum, lithium, sodium, calcium, manganese, preferably in metallic form.

12. The method according to any one of the preceding claims, characterized in that said mixture of components comprises a binder, preferably chosen from polymers.

13. The method of any preceding claim, wherein said mixture of components is a paste or viscous liquid comprising a solvent, said paste or viscous liquid being contacted with said anode, or said paste or viscous liquid being dried prior to contacting the dried component mixture with said anode or dried directly or following contact with said anode.

14. The method according to any one of the preceding claims, in which the step of adding a separator and / or a liquid and / or solid electrolyte is absent.

15. The method according to any one of the preceding claims, wherein said cathode active material, said conductive material and, where appropriate, said binder, are chosen from in such a way as to allow the presence in amorphous form and / or in complexed form and / or in micronized form in the state of fine particles of the salts added to the mixture of components.

16. The method of any preceding claim, wherein said cathode active material and said reactive agent are different materials which are preferably pre-mixed before being added and / or mixed with said conductive material.

17. The method according to any one of the preceding claims, wherein said cathodic mixture of components has a temperature below 150°C, preferably below 100°C, when contacted with said anode, and / or wherein the step of said contacting is carried out at a temperature which is below 150°C, preferably below 100°C.

18. The method of any preceding claim, wherein said cathodic mixture of components has a temperature below 50°C when contacted with said anode, and / or wherein the step of said contacting is carried out at a temperature which is below 50°.

19. A battery obtained according to the method according to any one of the preceding claims.

20. An assembly for assembling a battery, the assembly comprising an anode and a cathode mixture of components comprising a cathode active material and a reactive agent, said mixture of components preferably providing at least the constituents of a cathode, and said mixture of components comprising at least one conductive material, characterized in that a cation selected from the cations of magnesium, iron, zinc, aluminum, nickel, lithium, sodium, potassium, calcium, manganese, indium, vanadium, zirconium, lanthanum, boron, silicon, cobalt, tin, titanium, hydrogen, and / or an anion selected from the anions of oxygen, sulfur, phosphate, chloride, fluoride, iodide, bromide, sulfate, acetate, nitrate, and organic anions is present in the mixture of components, preferably in said reactive agent, said assembly allowing the preparation of a battery following contacting of the anode with a cathode formed from said cathode mixture of components.

21. A battery without liquid electrolyte and / or a solid-state battery comprising a cathode, an anode, a separator of the solid-electrolyte interface (SEI) type, the cathode comprising a cathodic mixture of components comprising an active cathode material and a reactive agent, said mixture of components preferably providing at least the constituents of a cathode, and said mixture of components comprising at least one conductive material.

22. The battery according to claim 21, characterized in that the anode comprises magnesium, preferably magnesium metal.

23. The battery according to claim 21, characterized in that the anode comprises one or more chosen from iron, zinc, aluminum, lithium, sodium, calcium, manganese, preferably in metallic form.

Images