Novel all-solid-state electrolytes based on organoboron covalent organic networks

Abstract

The present invention relates to an organoboron covalent organic network impregnated with at least one salt selected from alkali metal salts and alkaline-earth metal salts, wherein the impregnated organoboron covalent organic network is substantially free of organic solvent. The present invention also relates to a method for preparing such an impregnated organoboron covalent organic network, the use thereof as a solid electrolyte in an all-solid-state battery, and a separator for an all-solid-state battery, an electrode for an all-solid-state battery and an all-solid-state battery comprising such an impregnated organoboron covalent organic network.

Description

[0001]New all-solid-state electrolytes based on organoboron covalent organic networks The present invention relates to an organoboron covalent organic network (or organoboron COF) impregnated with at least one salt, selected from alkali metal salts and alkaline earth metal salts. The present invention also relates to a method for preparing such an impregnated organoboron covalent organic network. The present invention further relates to the use of such an impregnated organoboron covalent organic network as a solid electrolyte in an all-solid-state battery, as well as to a separator for an all-solid-state battery, an electrode for an all-solid-state battery and an all-solid-state battery comprising such an impregnated organoboron covalent organic network. “Conventional” lithium batteries have high energy densities and are used in many everyday objects (e.g., electric vehicles, portable electronic devices).Lithium batteries are based on the reversible exchange of lithium ions between a positive and a negative electrode, the latter being separated by an ion-conducting electrolyte. Traditionally, electrolytes are organic solvents mixed with lithium salts. However, they have the disadvantages of being toxic, flammable, and potentially compromising battery safety, for example due to the risk of explosion. US 2019 / 284212 and CN 114094172 both describe organoboron covalent organic networks impregnated with a lithium salt, as well as a significant amount of organic solvent, which can be used as battery electrolytes. There is a need to develop safer batteries, while maintaining or even improving the performance of known batteries, particularly those with high ionic conductivity at operating temperature.Li-polymer batteries are currently a promising alternative for securing batteries while providing new properties (e.g., flexibility) and eliminating certain critical resources. PEO technology is one example of achievement in this field. However, although this technology has made it possible to build efficient batteries, current performance is limited by the operating temperature (60°C) and the recyclability of the electrolyte at the end of the battery's life. There is therefore a need for new all-solid-state electrolyte materials. In particular, there is a need for all-solid-state electrolyte materials with high ionic conductivity.In particular, there is a need for all-solid electrolyte materials having high ionic conductivity over a wide operating temperature range, it being understood that, for application as an ionic electrolyte, these materials must have the lowest possible electronic conductivity. There is also a need for all-solid electrolyte materials having better recyclability than current electrolytes. It has been discovered by the present inventors that, quite surprisingly, these objectives are achieved by a material with a particular structure, more precisely, a material based on an organoboron covalent organic network impregnated with a specifically chosen salt, and, unlike the ionic electrolyte materials proposed by the prior art, devoid of organic solvent. Nothing in the prior art suggested such a result.The present invention therefore relates to an organoboron covalent organic network impregnated with at least one salt selected from alkali metal salts and alkaline earth metal salts. The present invention more particularly relates to an organoboron covalent organic network impregnated with at least one salt selected from alkali metal salts and alkaline earth metal salts, the impregnated organoboron covalent organic network being substantially free of organic solvent. A covalent organic network corresponds to the French translation of the English term "covalent organic framework", or COF. A covalent organic network is a porous and crystalline, two- or three-dimensional material, prepared by connecting light elements (for example, B, C, N, O) by covalent bonds in a periodic manner. A covalent organic network is therefore composed of a periodically repeated elementary unit.An organoboron compound is, according to the invention, an organic compound comprising at least one bond between a carbon atom and a boron atom. An organoboron covalent organic network according to the invention is therefore a covalent organic network whose elementary unit comprises at least one boron atom. According to the invention, the term “substantially free of organic solvent” means that the impregnated organoboron covalent organic network comprises less than 5% by weight of organic solvent relative to the total weight of the impregnated organoboron covalent organic network, preferably less than 2% by weight, preferably less than 1% by weight, preferentially less than 0.5% by weight, more preferentially less than 0.1% by weight. Advantageously, the impregnated organoboron covalent organic network is completely free of organic solvent.In the context of the present invention, the term organic "solvent" includes ionic liquids, which, as known to those skilled in the art, have all the characteristics required for the characterization of a substance as an organic solvent. The organic solvent is, for example, polar. The organic solvent is, for example, acetone, ethyl acetate, acetonitrile, dimethylformamide, dimethoxyethane, dioxane, triethylamine, tetrahydrofuran, dimethyl sulfoxide, NN-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-octylpyrrolidone, methanol, ethanol, isopropyl alcohol, diethyl ether, diisopropyl ether, methyltert-butyl ether, methyltetrahydrofuran or 2-ethoxy-2-methylpropane. The impregnated organoboron covalent organic network according to the invention is in particular substantially free of tetrahydrofuran.According to the invention, the term "substantially free of tetrahydrofuran" means that the impregnated organoboron covalent organic network comprises less than 5% by weight of tetrahydrofuran relative to the total weight of the impregnated organoboron covalent organic network, preferably less than 2% by weight, preferably less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight. Advantageously, the impregnated organoboron covalent organic network is completely free of tetrahydrofuran. The impregnated organoboron covalent organic network according to the invention is furthermore substantially free of ionic liquid.According to the invention, the term "substantially free of ionic liquid" means that the impregnated organoboron covalent organic network comprises less than 5% by weight of ionic liquid relative to the total weight of the impregnated organoboron covalent organic network, preferably less than 2% by weight, preferably less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight. Advantageously, the impregnated organoboron covalent organic network is completely free of ionic liquid. Preferably, the impregnated organoboron covalent organic network according to the invention has a specific surface area greater than or equal to 50 m² / g, preferably greater than or equal to 250 m² / g, preferably greater than or equal to 500 m² / g, and in particular greater than or equal to 500 m² / g.The specific surface area of ​​the impregnated organoboron covalent organic network according to the invention is preferably 50 to 3000 m² / g, preferably 400 to 1600 m² / g, and in particular 500 to 1600 m² / g. The specific surface area can be determined by N2 adsorption: the analysis of the N2 gas adsorption isotherms can be carried out using a Micromeritics ASAP 2020 porosimetry analyzer, a Micromeritics porosimetry analyzer. The measurement is carried out at 77 K (liquid N2 bath) on degassed and activated 300 mg samples. Preferably, the impregnated organoboron covalent organic network according to the invention has a pore diameter greater than or equal to 1.0 nm, preferably greater than or equal to 1.5 nm, preferably greater than or equal to 2.0 nm, preferably between 1.0 and 5.0 nm, preferably between 2.0 and 3.0 nm.The pore diameter can be determined from nitrogen adsorption isotherms, for example at 77 K, according to the BJH (Barret-Joyner-Halenda) method. Advantageously, the impregnated organoboron covalent organic network according to the invention degrades in the presence of water. When used as an electrolyte in a battery, this instability in the presence of water allows recycling of the electrolyte much easier than with the electrolytes of the prior art. Organoboron covalent organic network The covalent organic network is preferably two-dimensional or three-dimensional, preferably two-dimensional. Preferably, the organoboron covalent organic network corresponds to the following formula (I):. in which A is a mono- or polycyclic organoboron moiety, optionally substituted, Z is a mono- or polycyclic organic moiety, optionally substituted, and in which each AZ bond is a carbon-boron bond, or the organoboron covalent organic network corresponds to the following formula (II): in which A is a mono- or polycyclic organoboron moiety, optionally substituted, X is a mono- or polycyclic organic moiety, optionally substituted, and in which each AX bond is a carbon-boron bond, or the organoboron covalent organic network is a spiroborate and corresponds to the following formula (III): in which D is a mono- or polycyclic organic fragment, optionally substituted, R is a linear organic fragment, optionally substituted, and M' + is a cation selected from metal, alkali metal or alkaline earth metal cations, such as Li + , N / A + , K + , That2+ , Mg 2+ You are Al. 3+. By "optionally substituted" is meant throughout the present application preferably optionally substituted by at least one C1-C6 alkyl group, preferably C1-C3, the alkyl group being optionally interrupted by an oxygen atom and / or optionally comprising an anionic group, for example a carboxylate, sulfonate or phosphonate group, or a halogenated group, for example the trifluoromethanesulfonimide group. The organoboron covalent organic networks of formula (I) and (III) are two-dimensional and the organoboron covalent organic networks of formula (II) are three-dimensional. Preferably, the organoboron covalent organic network is of formula (I). Preferably, in formula (I), each AZ bond is a bond between a boron atom of fragment A and a carbon atom of fragment Z.Preferably, in formula (II), each AX bond is a bond between a boron atom of fragment A and a carbon atom of fragment X. Preferably, the organoboron covalent organic network consists of carbon, hydrogen, boron and oxygen atoms, and optionally silicon. According to the invention, a monocyclic compound is a compound comprising a ring, saturated or unsaturated, optionally comprising one or more heteroatoms, such as N or O. According to the invention, a polycyclic compound is a compound comprising at least two rings, each ring being independently saturated or unsaturated, fused (having at least 2 atoms in common) with one or more of the other rings and / or separated from the other ring(s) by at least one chemical bond, and optionally comprising one or more heteroatoms, such as N or O. Preferably, in formula (I), each AZ chemical bond forms a boronic ester function.Preferably, each AZ bond corresponds to a bond between a carbon of fragment Z and a boron of a B(O)2 unit of fragment A. Preferably, in formula (II), each AX chemical bond forms a boronic ester function. Preferably, each AX bond corresponds to a bond between a carbon of fragment X and a boron of a B(O)2 unit of fragment A. Preferably, in formula (I) or (II), fragment A is chosen from a fragment of formula (A-1). and a fragment of formula (A-2) wherein E is a mono- or polycyclic, optionally substituted, preferably aromatic, hydrocarbon fragment. Preferably, E is a fragment comprising one or more 6-membered hydrocarbon rings, each ring being independently saturated or comprising at least one unsaturation, preferably aromatic, and optionally substituted. Preferably, E comprises at least two 6-membered, optionally substituted aromatic hydrocarbon rings, each ring being independently fused (having 2 atoms in common) with one or more of the other rings and / or separated from the other ring(s) by at least one chemical bond. More preferably, E comprises at least three 6-membered, optionally substituted aromatic hydrocarbon rings, each ring being fused with at least one other ring, preferably with exactly one other ring.Advantageously, E comprises, preferably consists of, four 6-membered aromatic hydrocarbon rings, each ring being fused with at least one other ring, preferably with exactly one other ring. Advantageously, fragment A is chosen from a fragment of formula (A-1). and a fragment of formula (A-21) Preferably, in formula (I), Z is a fragment comprising one or more 6-membered hydrocarbon rings, each ring being independently saturated or comprising at least one unsaturation, preferably aromatic, and optionally substituted. Preferably, Z comprises one or more 6-membered aromatic hydrocarbon rings, optionally substituted, and when it comprises several rings, each ring is independently fused (have 2 atoms in common) with one or more of the other rings and / or separated from the other ring(s) by at least one chemical bond.More preferably, Z comprises, preferably consists of, 1 to 6, preferably 1 to 4, preferably 1, 2 or 3 6-membered hydrocarbon aromatic rings, each optionally independently substituted, and when it comprises several rings, each ring being separated from the other ring(s) by at least one chemical bond, preferably by 1, 2 or 3 chemical bonds, so as to form a linear chain of rings. Preferably, each ring is separated from the other rings by exactly one carbon-carbon chemical bond, or by 3 linearly chained chemical bonds, the second chemical bond being a carbon-carbon or carbon-nitrogen double bond. Advantageously, the fragment Z is chosen from a fragment of formula (Z-1). a fragment of formula (Z-2), a fragment of formula (Z-3), and a fragment of formula (Z-3'): . Preferably, in formula (II), X is a fragment comprising one or more 6-membered hydrocarbon rings, each ring being independently saturated or comprising at least one unsaturation, preferably aromatic, and optionally substituted. Preferably, X comprises at least two, preferably from two to four 6-membered aromatic hydrocarbon rings, optionally substituted, each ring being separated from the other ring(s) by at least one chemical bond, preferably all being connected to the same tetravalent atom, preferably to the same carbon or silicon atom. More preferably, X comprises, preferably consists of, four 6-membered aromatic hydrocarbon rings, each ring being at the same tetravalent atom, preferably to a carbon or silicon atom. Advantageously, the fragment X is a fragment of formula (X-1): in which G is a carbon atom or a silicon atom.Preferably, in formula (III), D is a fragment comprising one or more 5- or 6-membered hydrocarbon rings, each ring being independently saturated or comprising at least one unsaturation, and optionally substituted. Preferably, D comprises 2 or 3 5- or 6-membered rings, each ring being independently fused (having 2 atoms in common) with one or more of the other rings. Advantageously, D is a fragment of formula (G-1):. Preferably, in formula (III), R is a saturated linear hydrocarbon fragment or one comprising at least one unsaturation, comprising from 1 to 6 carbon atoms, preferably from 2 to 4, advantageously 2 carbon atoms. Advantageously, R is the group –C≡C–. Preferably, the organoboron covalent organic network is selected from COF-1, COF-5, COF-10, COF of formula (I) in which A = (A-1) and Z = (Z-3), COF of formula (I) in which A = (A-1) and Z = (Z-3'), COF of formula (I) in which A = (A-21) and Z = (Z-3), COF of formula (I) in which A = (A-21) and Z = (Z-3'), COF-102 (formula (II) with A = (A-1), X = (X-1) and G = C), COF-103 (formula (II) with A = (A-1), X = (X-1) and G = Si), COF-105 (formula (II) with A = (A-21), X = (X-1) and G = Si), COF-108 (formula (II) with A = (A-21), X = (X-1) and G = C) and COF spiroborate of the following formula (III-A): in which M' +is a cation selected from metal, alkali metal or alkaline earth metal cations, such as Li + , N / A + , K + , That 2+ , Mg 2+ or Al 3+. The structures of the organoboron covalent organic networks COF-1, COF-5, COF-10, COF-102, COF-103, COF-105 and COF-108 are well known to those skilled in the art. More preferably, the organoboron covalent organic network is chosen from COF-1, COF-5 and COF-10, preferably is COF-5. COF-1 is an organoboron covalent organic network of formula (I) in which A is of formula (A-1) and Z is of formula (Z-1) as defined above. COF-5 is an organoboron covalent organic network of formula (I) in which A is of formula (A-21) and Z is of formula (Z-1) as defined above. COF-10 is an organoboron covalent organic network of formula (I) in which A is of formula (A-21) and Z is of formula (Z-2) as defined above. Salt The impregnated organoboron covalent organic network according to the invention comprises at least one salt. This salt is chosen from alkali metal salts and alkaline earth metal salts.It is preferably an alkali metal salt, preferably a lithium salt. Preferably, the salt is a salt of formula MX1, M being a metal cation chosen from alkali metal cations and alkaline earth metal cations, and X1 being an anion comprising at least one halogen. Preferably, M is a cation chosen from Li. + , N / A + , K + , Mg 2+ and that 2+ , advantageously is Li +. Preferably, X1 is chosen from halide ions, preferably Br- or I-, advantageously I-, the perchlorate anion ClO4-, the bis(trifluoromethanesulfonyl)imide anion (known by the acronym TFSI), the bis(fluorosulfonyl)imide anion (known by the acronym FSI), the hexafluorophosphate anion PF6-, the tetrafluoroborate anion BF4-, the bis(pentafluoroethanesulfonyl)imide anion (known by the acronym BETI), the C1-C4 fluoroalkyl-4,5-dicyanoimidazolate anions, for example the trifluoromethyl-4,5-dicyanoimidazolate anion or the pentafluoroethyl-4,5-dicyanoimidazolate anion, more preferably halide ions, preferably Br- or I-, more preferably I-, the perchlorate anion ClO4- and the bis(trifluoromethanesulfonyl)imide anion. Advantageously, X1 is the I- ion. The salt is preferably lithium iodide.According to another embodiment, the salt is an ammonium ion salt, preferably a quaternary ammonium salt, preferably a C1-C4 tetraalkyl ammonium salt, such as a tetramethyl ammonium salt, or a phosphonium ion salt, preferably a quaternary phosphonium salt, preferably a C1-C4 tetraalkyl phosphonium salt, such as a tetramethyl phosphonium salt. Preferably, according to this embodiment, the anion of the salt is a halide ion, preferably the iodide ion. Preferably, the impregnated organoboron covalent organic network according to the invention has a molar ratio between the molar quantity of alkali metal or alkaline earth metal, and the total molar quantity of boron in the impregnated organoboron covalent organic network, of between 0.05 and 10, preferably between 0.1 and 5, preferably between 0.2 and 4, preferentially between 0.3 and 3.The molar quantities of alkali metal or alkaline earth metal and the molar quantity of boron are defined in relation to the total quantity of moles in the impregnated organoboron covalent organic network, i.e. the molar quantity of boron taken into account for the calculation of the ratio includes the boron contained in the organoboron covalent organic network and the boron possibly contained in the salt.The present invention also relates to a method for preparing an impregnated organoboron covalent network according to the invention, comprising the following steps: - a step of providing an organoboron covalent network, - a step of adding to the organoboron covalent network a salt chosen from alkali metal salts and alkaline earth metal salts, said salt being in solution in an organic solvent, and obtaining a mixture, - a step of stirring the mixture, and - a step of removing, totally or substantially totally, the organic solvent by drying the mixture, said drying being divided into at least a first drying step and a second drying step. The organoboron covalent network and the salt are preferably as defined above with regard to the impregnated organoboron covalent network.Preferably, the stirring step is carried out for at least 120 hours, preferably at least 144 hours, preferably at least 168 hours, preferably between 120 hours and 340 hours. The step of removing the organic solvent is preferably carried out directly on the mixture, in particular without prior mechanical treatment of the latter, such mechanical treatment preferably also not being carried out between the first drying step and the second drying step. Preferably, at least one step among the first drying step and the second drying step is carried out at a temperature of between 30°C and 230°C, preferably between 30°C and 180°C, preferably between 40°C and 150°C, preferably between 50°C and 130°C, preferably between 60°C and 120°C. Preferably, the first drying step is carried out at a temperature between 15°C and 30°C, preferably around 25°C.Preferably, the first drying step is carried out under reduced pressure. Preferably, the first drying step is carried out under an inert atmosphere. Preferably, the first drying step is carried out for 5 hours to 36 hours, preferably for 6 hours to 24 hours, preferably for 10 hours to 20 hours. Preferably, the second drying step is carried out at a temperature between 40°C and 180°C, preferably between 50°C and 150°C, preferably between 60°C and 130°C. Preferably, the second drying step is carried out under reduced pressure. Preferably, the second drying step is carried out under an inert atmosphere. Preferably, the second drying step is carried out for 2 hours to 12 hours, preferably for 4 hours to 10 hours, preferably for 5 hours to 7 hours. Preferably, the drying further comprises a third drying step.Preferably, the third drying step is carried out at a temperature between 80°C and 180°C, preferably between 100°C and 150°C, preferably between 110°C and 130°C. Preferably, the third drying step is carried out under reduced pressure. Preferably, the third drying step is carried out under an inert atmosphere. Preferably, the third drying step is carried out for 8 hours to 48 hours, preferably for 10 hours to 36 hours, preferably for 12 hours to 20 hours. According to this embodiment, the second drying step is preferably carried out at a temperature between 30°C and 100°C, preferably between 40°C and 90°C, preferably between 50°C and 80°C, preferably between 60°C and 70°C. Preferably, the second drying step is carried out under reduced pressure. Preferably, the second drying step is carried out under an inert atmosphere.Preferably, the second drying step is carried out for 2 hours to 12 hours, preferably for 4 hours to 10 hours, preferably for 5 hours to 7 hours. By "under reduced pressure" is meant under a pressure of between 1 mbar and 50 mbar, preferably between 3 mbar and 30 mbar, preferably between 5 mbar and 15 mbar. By "under an inert atmosphere" is meant preferably under an atmosphere comprising between 0.1 ppm and 10 ppm of O2 and / or between 0.1 and 10 ppm of water. The organic solvent is preferably polar. The polar solvent is preferably different from tetrahydrofuran. The organic solvent preferably has a boiling point at atmospheric pressure of less than or equal to 65°C, preferably between 30°C and 60°C, and / or a vapor pressure at 20°C of greater than 20 kPa, preferably between 23 and 40 kPa.The organic solvent is for example chosen from acetone, ethyl acetate, acetonitrile, dimethoxyethane, dioxane, NN-dimethylacetamide, N-ethyl-2-pyrrolidone, and N-octylpyrrolidone, methanol, ethanol, isopropyl alcohol, diethyl ether, diisopropyl ether, methyltert-butyl ether, methyltetrahydrofuran or 2-ethoxy-2-methylpropane, advantageously is acetone. The present invention also relates to the use of an impregnated organoboron covalent network according to the invention as a solid electrolyte in an all-solid-state battery. Preferably, the impregnated organoboron covalent network is used as a separator and / or as an electrolytic material of an all-solid-state battery electrode.The all-solid-state battery may be a Li-ion, primary Li (non-rechargeable) and Li metal (rechargeable or not), dual-ion double electrolyte, Na-ion, K-ion, Mg-ion or Ca-ion, or Na-metal battery, preferably in a Li-ion, primary Li and Li metal battery. When used in a separator, the impregnated organoboron covalent network may be used alone or in conjunction with one or more additional compounds, for example a binder, preferably polymeric. When used as an electrolytic material of an all-solid-state battery electrode, the impregnated organoboron covalent network may be used in conjunction with one or more additional compounds conventionally used, for example a positive or negative electrode active material, and optionally a binder and / or a conductive additive.Said electron-conducting additive(s) may be chosen from carbon fibers, carbon black, carbon nanotubes, graphite, graphene, acetylene black and their analogues, metal particles, for example silver or copper particles, conductive polymers, for example poly-p-phenylene, poly(3,4-ethylenedioxythiophene) (PEDOT), polyaniline (PANI) or polypyrrole, and charge transfer complexes, for example those of the tetrathiofulvalenium-tetracyanoquinodimethane (TTF-TCNQ) type. The binder(s) may be chosen from fluorinated binders, in particular polytetrafluoroethylene and polyvinylidene fluoride, cellulose fibers, cellulose derivatives such as starch, carboxymethylcellulose and its derivatives, polysaccharides and latexes, in particular of the styrene-butadiene rubber type. The electrode can be a positive electrode or a negative electrode.The term "negative electrode" refers to the electrode functioning as an anode when the accumulator is discharging, and the term "positive electrode" refers to the electrode functioning as a cathode when the accumulator is discharging. Said positive electrode active material(s) are not particularly limited, and may be chosen from: - materials capable of reversibly inserting lithium ions which may be chosen from oxides such as Li. x MO2(0.5 ≤ x ≤ 3), in which M represents at least one metallic element selected from the group comprising Ni, Co, Mn, Fe, Cr, Ti, Cu, V, Al and Mg and vanadates such as LixV2O5(0 ≤ x ≤ 5) or Li XV3O8(1 ≤ x ≤ 3), phosphates such as LiFePO4, Li3Fe2(PO4)3, LiV2(PO4)3, ; silicates such as Li2FeSiO4, borates such as LiFeBO3 and sulfonates such as LiFeSO4F, Li2Fe2(SO4)3 - materials capable of reversibly inserting lithium ions which can be chosen from oxides of formula Li 1+y+z / 3 You 2-z / 3 O4(0 < z <1, 0 < y <1), Li 4+z' Ti5O 12(0 <z'<3), le carbone et les produits carbonés provenant de la pyrolyse de matières organiques, ainsi que les carboxylates organiques tels que les terephthalates ; - les matériaux organiques d’électrodes, tel que la benzoquinone et ses dérivés, le 7,7,8,8-tétracyano-p-quinodiméthane et ses dérivés, les oximates, les sulfonimide, les perylènes diimides et dianhydrides. Ledit ou lesdits matériaux actifs d’électrode négative ne sont pas particulièrement limités, et peuvent être choisis parmi les matériaux en carbone, en particulier le carbone dur, le carbone mou, les nanofibres de carbone ou le feutre de carbone, l'antimoine, l'étain et le phosphore. La présente invention concerne également l’utilisation d’un réseau covalent organoboré imprégné selon l’invention comme additif dans une composition d’électrolyte.The electrolyte composition may comprise: - a solution of an alkali or alkaline earth metal salt, said salt being as defined above, for example LiI, the salt being in solution in a solvent conventionally used in electrolyte compositions, for example N-methylpyrrolidone (NMP) or acetone, or - an oxygenated polymer such as polyethylene oxides, PEO (5-100000), a polymer including an immobilized trifluoromethylsulfonylimide (TFSI) fragment, such as poly(4-styrenesulfonyl(trifluorosulfonyl)imide) (PSTFSI), or - a sulfide-type ceramic material such as argyrodite. The presence of the impregnated organoboron covalent network according to the invention in the electrolyte composition advantageously allows an improvement in the electrochemical performances of the composition.For example, when the impregnated organoboron covalent network is associated with a conductive polymer, cooperation is observed, in particular in terms of conductivity, between the impregnated organoboron covalent network and the conductive polymer. The present invention therefore also relates to an electrolyte composition comprising an impregnated organoboron covalent organic network according to the invention. This composition may, in addition to the impregnated organoboron covalent organic network, further comprise a solution of alkali or alkaline-earth metal salt, an oxygenated polymer or a ceramic material as defined above concerning the use as an additive of an impregnated organoboron covalent network according to the invention. Preferably, the composition comprises at least 0.2% by weight of the impregnated organoboron covalent organic network relative to the total weight of the composition, preferably an amount greater than or equal to 0.5% by weight, preferably between 0.5% and 50% by weight.The present invention therefore also relates to a solid separator for an all-solid-state battery comprising an impregnated organoboron covalent network according to the invention. The separator according to the invention is as defined above. The present invention therefore also relates to an electrode for an all-solid-state battery comprising an impregnated organoboron covalent network according to the invention. The electrode may be positive or negative. The positive electrode comprising the impregnated organoboron covalent network according to the invention further comprises a positive electrode active material, and optionally a binder and / or a conductive additive. These components are as defined above. The negative electrode comprising the impregnated organoboron covalent network according to the invention further comprises a negative electrode active material, and optionally a binder and / or a conductive additive. These components are as defined above.The positive or negative electrode may further comprise a current collector, for example an aluminum or copper foil, or a layer of carbon or conductive polymer, such as poly(3,4-ethylenedioxythiophene). The present invention further relates to an all-solid-state battery comprising an impregnated organoboron covalent network according to the invention. The all-solid-state battery may be a Li-ion, primary Li (non-rechargeable), Li metal (rechargeable or not), dual-ion double electrolyte, Na-ion, K-ion, Mg-ion, Ca-ion or Na-metal battery, preferably in a Li-ion, primary Li and Li metal battery. An all-solid-state battery comprises a positive electrode, a negative electrode and a separator. As explained above, the impregnated organoboron covalent network according to the invention may be present in the separator of the battery and / or in the positive electrode and / or in the negative electrode. These elements are independently as defined above.The invention will now be described using non-limiting examples. FIGURES Figure 1 is a set of FT-IR spectrograms (between 500 and 1750 cm. -1 ) compared between (from top to bottom): ABDB, COF-5, lithium salt and COF-5 impregnated with said lithium salt (molar ratio Li / B = 1), for the cases where the lithium salt is a) LiClO4, b) LiBr c) LiTFSI and d) LiI. Figure 2 is a set of FT-IR spectrograms (between 500 and 4000 cm -1) compared between (from top to bottom): ABDB, COF-5, lithium salt and COF-5 impregnated with said lithium salt (molar ratio Li / B = 1), for the cases where the lithium salt is a) LiClO4, b) LiBr c) LiTFSI and d) LiI. Figure 3 is a set of compared FT-IR spectrograms of COF-1 and COF-1 impregnated with LiI (Li / B ratio = 2). Figure 4 is a set of compared FT-IR spectrograms of COF-10 and COF-10 impregnated with LiI (Li / B ratio = 2). Figure 5 is a set of EIS spectrograms of COF-5-based impregnated organoboron covalent networks as a function of the Li / B ratio, in the case where the lithium salt is a) LiClO4 (left) or b) LiTFSI (right). Figure 6 is a set of EIS spectrograms of COF-1 or COF-5-based organoboron covalent networks impregnated with LiI (Li / B molar ratio = 2), and comparison with LiI alone.Figure 7 is a set of EIS spectrograms of organoboron covalent networks based on COF-10 or COF-5 and impregnated with LiI (molar ratio Li / B = 2), and comparison with LiI alone. Figure 8 is two galvanostatic cycling curves of a battery comprising a lithium salt-based solid electrolyte in which the separator comprises the COF impregnated COF-5@LiI (left), or in which the separator comprises only LiI (right). Figure 9 is a galvanostatic cycling curve of a Li-metal / organic polymer battery (Li-TCNQ as positive electrode) according to Example 4. Figure 10 is a galvanostatic cycling curve of a Li-metal / organic COF- 5@LiI battery (Perylene diimide as positive electrode) according to Example 4. Figure 11 shows Fourier transform infrared (FT-IR) spectra obtained respectively for a COF-5 organoboron covalent network with a specific surface area of ​​2068 m. 2 / g (“COF-5 h”) and a covalent organoboron network COF-5 with a specific surface area of ​​405 m 2 / g (“COF-5 l”). Figure 12 shows spectra obtained by electrochemical impedance spectroscopy, at different temperatures (20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C and 100°C) for a covalent organoboron network COF-5 with a specific surface area of ​​405 m 2 / g impregnated with LiI. EXAMPLES Methods for analyzing organoboron covalent networks and organoboron covalent networks impregnated according to the invention Infrared (IR) spectroscopy The infrared spectra were recorded on a Shimadzu 8400S FTIR spectrometer using an attenuated total reflection analysis accessory (transmission mode - KBr). The infrared spectra were collected between 4000 cm -1 and 500 cm -1. Atomic Absorption Lithium content measurements in impregnated organoboron covalent networks were performed by atomic absorption using the PERKIN ELMER Analyst 300 spectrometer at a wavelength of 670.8 nm. A neon-filled hollow cathode (lithium) lamp was used as a source, as well as a flame generated by a mixture of air and acetylene for atomization. A direct calibration was performed with three concentration solutions at 1, 2 and 3 ppm prepared from a commercial standard solution at 1 mol.L -1 in Li + The sample was prepared in such a way as to obtain a concentration of 2 ppm in Li + , then analyzed as an unknown concentration. The absorbance value obtained is plotted against the calibration curve previously prepared to obtain the actual Li concentration +and therefore the lithium level associated with the compound. Each sample was analyzed three times to validate the lithium level found. NMR The spectrometer used is the BRUKER AVANCE III HD 500 MHz SB equipped with a CP_MAS solid probe and an 11.7 T Ultra Shield magnet. The samples are loaded into a 4 mm ZrO2 rotor. The NMR spectra 13 C , 11 B and 7 Cross-polarized magic angle Li (CP-MAS) were recorded at a rotation rate of 15 kHz. The chemical shifts of the 13C are referenced to hexamethylbenzene at 17.3 ppm as a standard. BET The analysis of N2 gas adsorption isotherms was carried out using a Micromeritics ASAP 2020 porosimetry analyzer, a porosimetry analyzer from Micromeritics. The measurement was carried out at 77 K (liquid N2 bath) on 300 mg samples degassed and activated before and after lithium salt impregnation. Example 1: Preparation of different organoboron covalent networks Different organoboron covalent networks were prepared according to the following protocols 1.1. Synthesis of COF-5 In a 500 ml two-necked flask were added 784 mg of hexahydroxytriphenylene (HHTP, supplier: TCI) and 602 mg of benzene diboronic acid (ABDB, supplier: Sigma Aldrich, Merck), previously ground and dried under vacuum at room temperature overnight. To this mixture was added 1.47 mL of methanol, then a 1:4 mixture of mesitylene: anhydrous 1,4-dioxane of 301 mL.The flask is then placed in an ultrasonic bath for 10 min and then heated to 90°C with vigorous stirring (≤ 500 rpm) for 7 days. The greenish-grey precipitate obtained is filtered, washed with anhydrous acetone and toluene. The powder is then dried under vacuum for 6 hours, then at 70°C for 6 hours and finally at 120°C for 12 hours in a Buchi programmable vacuum tube furnace. IR and NMR analyses of the product obtained give the following results: IR (KBr pellet) (cm. -1 ): 1522; 1491; 1450 υ(C=C); 1350 υ(BO); 1324 υ(BO); 1240 υ(C-O); 1161 υ(CH); 1077 υ(CH); 1026 υ(BC); 849 υ(CH); 832; 657; 612 NMR CP MAS 13 C δ in ppm: 146.72 (CO); 132.8 (CB); 123.85 (C=C); 102.98 (C-HAr) NMR CP MAS 11B δ in ppm: 21.07 (BO), 13.83 (BC) 1.2. Synthesis of COF-1 In a dry two-neck flask were introduced 200 mg of benzene 1,4-diboronic acid (sigma aldrich, Merck), previously ground by hand and then dried at room temperature under vacuum overnight, 40 ml of 1:1 v:v of a mixture of methylene and 1,4-dioxane was added under an inert atmosphere (argon). The mixture was put in an ultrasonic bath for 5 min then bubbled for 30 min and finally heated at 80°C for 72h. A white powder is obtained by centrifugation washed with anhydrous acetone then dried at 65°C for 6h then 6h at 120°C under BUCHI (Yield 82%). IR (KBr pellet) (cm -1 ): 1509 υ(C=C); 1398 υ(BO); 1339 υ(BO); 1301 υ(CC); 1107 υ(C-H); 1019 υ(CH); 711 υ(B3O3); NMR CP MAS 13 C δ in ppm: 133;127 NMR CP MAS 11B δ in ppm: 31.82; 32.89. 1.3. Synthesis of COF-10 112 mg of HHTP (TCI), 86 mg of biphenyl diboronic acid ABPD (sigma aldrich, Merck) previously ground by hand then dried at room temperature under vacuum overnight and 0.21 ml of MeOH were introduced into a flask. The mixture is dissolved in 43 mL of a 1:4 mesitylene:dioxane mixture and then placed in an ultrasonic bath for 1 min and then heated at 90°C with vigorous stirring for 7 days. The solid is isolated by filtration and briefly washed with toluene and then with anhydrous acetone. The solid is dried under vacuum at 120°C overnight (Yield 79%). IR (KBr pellet) (cm -1 ): 1492; 1449; 1353; 1326; 1241; 1159; 1017; 1006; 848; 834, 810; 726;650 NMR CP MAS 13 C δ in ppm: 146.62; 141.38; 134.40; 123.90 RMN CP MAS 11B δ in ppm: 1.09. 1.4. Synthesis of imine-boroxine-COF-1 300 mg of formylphenyl-4-boronic acid (FPBA) and 108 mg of 1,4-phenylenediamine (PDA) were introduced into a 100 mL flask in a 1 / 3 v / v solution (40 mL) of 1,4-dioxane / mesitylene. The mixture was placed in an ultrasonic bath for 10 min and then treated by flash freezing at 77K. The mixture was then degassed under vacuum until it thawed. The operation was repeated 3 times. The reaction mixture was then heated at 120°C for 3 days. An orange-brown precipitate was collected by filtration and then washed with anhydrous acetone. The product is then immersed in dichloromethane for 3 days, during which time the activation solvent was decanted and replaced freshly four times. The orange-brown precipitate obtained is dried at room temperature and then at 100°C under vacuum overnight (Yield.78%). IR (KBr pellet) (cm -1) : 1656 uC=O) ; 1626 u(C=N) ; 1497 u(CH) ; 1441 ; 1315 u(B- O) 1216 u(BC) ; 1019 u(CH) ; 1011 ; 870 ; 710 u(B3O3) ; 631 ; 532 ; 504 ; 474 ; 442 RMN CP MAS 13 C δ en ppm : 159 (C=N); 150 (C Ar -N) ;139 (C Ar -C=) ; 127 (CB) ; 116 (C Ar- H). 1.5. Synthesis of imine-boronate-COF-2 A 1 / 3 v / v solution (40 mL) of 1,4-dioxane / mesitylene containing 270 mg of formylphenyl-4-boronic acid, 105 mg of 1,4-phenylenediamine and 195 mg of hexahydroxytriphenylene is introduced into a 100 mL flask. The flask is placed in an ultrasonic bath for 10 min and then quickly frozen at 77K. The mixture is then degassed under vacuum until it thaws. The operation is repeated 3 times. The reaction mixture is then heated at 120°C for 3 days. A greenish precipitate is collected by filtration and then washed with anhydrous acetone. The product is then immersed in dichloromethane for 3 days, during which time the activation solvent was decanted and replaced freshly four times. The greenish-brown precipitate obtained is dried at room temperature and then at 100°C under vacuum overnight (yield 79%). IR (KBr pellet) (cm -1) : 1688 u(C=O) ; 1608 u(C=N) ; 1491 u(CH) ; 1445 ; 1353 u(BO) ; 1325 u(BO) ; 1241 u(CO) ; 1160 ; 1062 u(BC) ; 1015 ; 976 ;856 ;845 ;728 RMN CP MAS 13 C δ en ppm : 157 (C=N); 149 (C Ar -N) ;139 (C Ar -C=) ;134 (C Ar -H) ; 124 (C Ar =C Ar ), 107 (C Ar-H). 1.6. Synthesis of imine-boroxine-COF-1 SO3Li 300 mg of FPBA (Sigma Aldrich, Merck) and 195.22 mg of lithium 1,4-phenylenediamine-2-sulfonate (PaSO3Li) dissolved in 40 mL of 1,4-dioxane / mesitylene (1 / 3 v / v) were introduced into a 100 mL round-bottomed flask. The mixture was placed in an ultrasonic bath for 10 min and then frozen at 77K. The mixture was then degassed under vacuum until it thawed. The operation was repeated 3 times. The reaction mixture was then heated at 120°C for 3 days. An orange precipitate was collected by filtration and then washed with anhydrous acetone. The product was then immersed in DCM for 3 days, during which time the activation solvent was decanted and replaced freshly four times. The orange-brown precipitate obtained was dried at room temperature and then at 100°C under vacuum overnight (Yield 62%). IR (KBr pellet) (cm -1): 1656 u(C=O); 1626 u(C=N); 1497 u(CH); 1441; 1315 u(BO); 1155 u(S=O); 1019; 1011; 870 u(SO); 833 u(SO) ; 711 u(B3O3) ; 631 ; 532 ; 504 ; 474 ; 442 RMN CP MAS 13 C δ en ppm: 159 (C=N) ; 146 (CN) ; 139 (CC Ar); 127 (CB); 117 (C=CH). 1.7. Synthesis of imine-boronate-COF-2 SO3Li In a 100 mL round-bottomed flask were introduced 451 mg of FPBA, 169 mg of lithium 1,4-phenylenediamine-2-sulfonate and 195 mg of hexahydroxytriphenylene, dissolved in 40 mL of 1,4-dioxane / mesitylene (1 / 3 v / v). The mixture was placed in an ultrasonic bath for 10 min and then frozen at 77K. The mixture was then degassed under vacuum until it thawed. The operation was repeated 3 times. Then the reaction mixture was heated at 120°C for 3 days. A brown precipitate was collected by filtration and then washed with anhydrous acetone. The product is then immersed in DCM for 3 days, during which time the activation solvent was decanted and replaced freshly four times. The brown precipitate obtained is dried at room temperature and then at 100°C under vacuum overnight (yield 70%). IR (KBr pellet) (cm -1): 1602 υ(C=N); 1491 υ(CH); 1445; 1354 υ(BO); 1334 υ(BO); 1241 υ(CO); 1160 υ(S=O); 1106; 1062 υ(BC); 1015; 981; 833 υ(SO);728; 697; 652; 610 NMR CP MAS 13 C δ in ppm: 157 (C=N); 146 (CAr-N); 139 (CAr-C=); 132 (CAr-H); 124 (CAr=CAr); 103.98 (CAr-H). Example 2: Preparation of different impregnated organoboron covalent networks according to the invention 100 mg of dry and activated COF are introduced into pill boxes. The pill boxes are placed under vacuum, then solutions of different lithium salts prepared with 6 mL of anhydrous acetone are added. The nature and quantity of lithium salt are gathered in Table 1 below. The mixture is stirred for 7 days. The acetone is evaporated at room temperature under an inert atmosphere and then the different impregnated COF samples are dried under vacuum (approximately 10 mbar) at room temperature for 4 h, then at 65°C for 6 h and finally at 120°C for 14 h. Table 1 LiI (sigma aldrich, Merck), LiBr (sigma aldrich, Merck), LiClO4(TCI), LiTFSI (sigma aldrich, Merck). The Li / B molar ratio was determined by atomic absorption analysis of the impregnated organoboron covalent networks. They correspond to the Li / B ratios of the introduced reagents. Example 3: Characterizations of the impregnated organoboron covalent networks according to the invention The impregnated organoboron covalent networks of Example 2 were characterized by IR spectroscopy and compared with the spectrograms of the COF and the corresponding lithium salt taken each in isolation (see Figures 1 to 4). The different impregnated COFs were also analyzed by NMR spectroscopy. The results of these two analysis techniques are summarized below: - COF-5@LiClO4: IR (KBr pellet) (cm -1 ): 1522; 1494; 1448; 1395; 1348 υ(BO); 1329 υ(BO); 1243 υ(C-O); 1145 υ(Cl-O); 1110 υ(Cl-O); 1080 υ(BC); 1018; 853; 832; 655; 636; 626 NMR CP MAS 13C δ en ppm : 146.72 (CO) ; 133.02 (C Ar -B); 123.85 (C Ar =C Ar ) ; 103.08 (C Ar - H) RMN CP MAS 11 B δ en ppm : 21,38 ; 7,95 - COF-5@LiTFSI : IR (KBr pellets) (cm -1 ) : 1521 ; 1492 ; 1450 ; 1349 υ(BO) ; 1322 υ(BO) ; 1243 υ(CO) ; 1200 υ(CF) ; 1162 υ(CF) ; 1133 ; 1075 υ(BC) ; 1019 ; 851 ; 832 ; 657 ; 577 MRI CP MAS 13 C δ en ppm: 146.60 (CO); 133(CAr-B); 127.86; 123.85; 123.79 (C=C) ; 102.98 (C-HAr) MRI CP MAS 11 B δ en ppm : 21.69 ; 9.22 - COF-5@LiI : IR (KBr pellets) (cm -1 ) : 1523; 1491; 1449; 1350 υ(BO); 1322 υ(BO); 1240 υ(CO); 1159; 1077 υ(BC); 1019; 848; 832; 655 ; 613 MRI CP MAS 13 C δ en ppm : 146.62 (CO) ; 133.8 (CB) ; 123.76 (C=C) ; 102.88 (C-HAr) MRI CP MAS 11 B δ en ppm :20.64 ;7.01 MRI CP MAS 7 Li δ en ppm : 0.32 ; -4.03 (LiI) MRI CP MAS 127 I δ en ppm: 408 - COF-5@LiBr : IR (KBr tablets) (cm -1 ) :1523; 1491; 1451; 1350 υ(BO); 1324 υ(BO); 1240 υ(CO); 1159; 1077 υ(BC); 1021; 848; 832; 657; 611 - Imine-boroxine-COF-1@LiI: IR (KBr pellet) (cm -1 ): 1653 υ(C=O); 1622 υ(C=N); 1487 υ(CH); 1441; 1315 υ(B-O); 1216 υ(BC); 1019 υ(CH); 1011; 870; 710 υ(B3O3); 631; 533; NMR CP MAS 13 C δ in ppm: - Imine-boronate-COF-2@LiI: IR (KBr pellet) (cm -1 ): 1682;1612; 1491; 1448; 1350;1323; 1243; 1160; 1064; 1015; 976; 856; 845; 728; 547 NMR CP MAS 13 C δ in ppm: 159 (C=N); 147 (C Ar -N);137 (C Ar -C=) ;134 (C Ar -H); 124 (C Ar =C Ar ), 107 (C Ar -H). N2 gas adsorption isotherms were also carried out for some impregnated organoboron covalent networks of Example 2. From these curves, the specific surfaces, expressed in m² / g, were determined for each impregnated COF and indicated in Table 2 below. Table 2 Example 4: Electrochemical analyses of the impregnated organoboron covalent networks according to the invention Materials and methods Sample preparation All experiments were carried out under a dry argon atmosphere in a glove box (O2 and H2O < 3 ppm). The powders, dried at 120°C for 8 h, were cold pressed at approximately 120 MPa for 1 min to obtain pellets for the electrochemical tests, also called "electrolyte" in the rest of this example. These were carried out at 70°C, except for the electrochemical impedance spectroscopy measurements. Electrochemical impedance spectroscopy Electrochemical impedance spectroscopy (EIS) measurements were carried out with an MTZ-35 frequency response analyzer (BioLogic) coupled to an intermediate temperature system (ITS), controlling the sample temperature by Peltier effect.An electrolyte pellet with a diameter of 6 mm and a thickness of 0.7 mm is sandwiched between two blocking electrodes for the conductive ion (30 mg; 120 MPa). This metal / electrolyte / metal device allows to observe only the behavior of the electrolyte on the impedance spectrum (blocking electrode: Al). The AC impedance spectra are recorded in the frequency range 30 MHz to 0.1 Hz with an excitation signal of 0.05 V amplitude. The measurements are carried out between 20 °C and 100 °C in heating and cooling (1 °C / min), with a temperature stabilization lasting 15 min before each impedance measurement. The ionic conductivities (σ) were determined according to the following equation: σ. ionique = l / (R*A) after modeling and simulation of EIS data using the equivalent circuit model, where l is the pad thickness, R is the resistance, and A is the surface area in contact with the electrodes with A = πr 2and r is the radius. The activation energy (Ea) was determined from the slope of the Arrhenius plot. The device is mounted in a sample holder which is itself placed inside the hermetic cell (Controlled Environment Sample Holder, CESH, BioLogic). Cyclic and linear scanning voltammetry This type of measurement makes it possible to validate the correct functioning of the electrolyte in terms of conductivity of Li ions by observing the reversibility of the Li system ++ e- = Li around 0V but also its possible electrochemical degradation by evaluating the parasitic currents in oxidation and reduction visible over the entire range previously evaluated determined by linear sweep voltammetry. Linear sweep voltammetry (LSV) is a simple electrochemical technique. The linear sweep voltammetry method is similar to cyclic voltammetry, but instead of performing a linear cycle over the potential range in both directions, linear sweep voltammetry involves a single linear scan from the lower potential limit to the upper potential limit. This time, the thickness of the electrolyte was thinner than previously 100 μm, to avoid distortion of the voltammogram by ohmic drop effect. An asymmetric cell assembly of the type (-) Li 0 / electrolyte / stainless steel (+) was used, where the study of the reversible deposition of lithium metal takes place on the stainless steel which will be the positive terminal of the potentiostat. Typically a scanning speed of 0.1 mV s -1 in a voltage range of -0.5 to 5.0 V (relative to Li / Li+) was applied to obtain the different chronoamperograms. Study of the reversibility of the Li electrochemical system + / Li by galvanostatic cycling This measurement also makes it possible to validate the correct functioning of the electrolyte in terms of ionic conductivity of the Li ions by observing the reversibility of the Li system + + e- = Li around 0V. A symmetrical cell (Li 0 / electrolyte / Li 0 ) was cycled over several cycles between +15 mV and -15 mV at current densities 0.1 mA / cm 2 , 0.2 mA / cm 2 and 2 mA / cm 2. Here too the thickness of the electrolyte was about 100 μm. Results 1. Conductivity measurement Figures 5 to 7 represent the EIS spectrograms of impregnated organoboron covalent networks based on COF-5, COF-1 or COF-10, as a function of the Li / B ratio. Table 3 below lists the conductivity values ​​at 20°C and 100°C of different COFs impregnated according to the invention. Table 3 These results show that the impregnated organoboron covalent networks according to the invention exhibit conductivities that make them suitable as electrolytes in batteries. Some values ​​are comparable with those of other known electrolyte materials such as ceramic materials. 2. Battery Tests First, the impregnated COF-5@LiI was tested as a separator. The following two batteries were prepared: one whose electrolyte is composed solely of anhydrous LiI and the second which includes a layer of COF-5@LiI (2Li / B) in the center of the electrolyte composed of anhydrous LiI. Lithium metal and Li-TCNQ were used as the negative and positive electrodes, respectively. These two batteries were then tested in a potential-limited galvanostatic mode. Note that the battery having only LiI as electrolyte / separator shows no electrochemical activity (Figure 8 right).Conversely, the one including the object of the present invention displays the electrochemical trace of the positive electrode material, located at 2.4 / 3V vs Li (Figure 8 left). In a second step, a battery (Li-TCNQ and Li-metal as positive and negative electrode respectively) comprising COF-5@LiI as an additive was prepared by incorporating COF-5@LiI into a PEO-type polymer matrix. This battery was tested by potential-limit galvanic cycling. The curve obtained is shown in Figure 9. These results show that the presence of COF-5@LiI in the electrolyte facilitates the transport of lithium ions and makes it possible to obtain the electrochemical trace of the positive electrode material. In a third step, a battery (Perylene-diimide and Li-metal as positive and negative electrode respectively) comprising COF-5@LiI as a solid electrolyte (compressed pellet) was prepared.This battery was tested by potential-limit galvanostatic cycling. The curve obtained is shown in Figure 10. These results show that COF-5@LiI, used directly as an electrolyte, makes it possible to obtain the electrochemical trace of the positive electrode materials and therefore the design of a solid organic Li-metal battery. Example 5: Covalent organoboron network COF-5 with lower specific surface area impregnated with LiI Preparation of COF-5 1 g of HHTP (i.e. 3.08.10. -3 mol) and 0.770 g of ABDB (i.e. 4.63.10 -3mol) are ground together in a zirconia crucible before being dried overnight (80°C at reduced pressure). 3 ml of methanol (synthesis grade) then a 1:4 mesitylene:1,4-dioxane volume mixture (i.e. 77:307 ml) are added to the precursors. The flask is placed in an ultrasonic bath for 10 min then heated to 90°C with very vigorous stirring (well above 500 rpm). After 7 days of stirring, the reaction mixture is filtered. The recovered solid is then washed three times with acetone. The COF-5 obtained has a specific surface area of ​​405 m 2 / g. The FT-IR spectrum obtained for this COF is shown in Figure 11 ("COF-5 l"). For comparison, this figure also shows the FT-IR spectrum of a COF-5 as obtained according to the protocol described in point 1.1 above, with a specific surface area of ​​2068 m 2 / g. Impregnation with LiI COF-5 is impregnated with a lithium iodide solution, to obtain a surface dispersion on the COF of 0.83 mg of LiI per m². For this purpose, 168.1 mg of lithium iodide are used for 1 g of COF. The impregnation protocol is identical to that described above. As a reminder, the LiI is dissolved in 7 ml of dry acetone. The COF-5 is suspended under stirring for 7 days in this solution and the solvent is then evaporated. The compound is rigorously dried under vacuum in several stages as described above. The Li / B ratio of the impregnated COF obtained is equal to 0.2. Conductivity measurements by electrochemical impedance spectroscopy The resistivity measurements, carried out as described in Example 4 above, reveal the absence of conductivity at 20°C and 30°C. The conductivity is observed, and becomes measurable, from 40°C and up to 100°C. The values ​​obtained are between 9.81.10 -9 S.cm -1(at 40°C) and 3.95.10 -6 S.cm -1 (100°C).

Claims

CLAIMS 1. An organoboron covalent organic network impregnated with at least one salt selected from alkali metal salts and alkaline earth metal salts, the impregnated organoboron covalent organic network being substantially free of organic solvent.

2. An impregnated organoboron covalent organic network according to claim 1, wherein the salt is a lithium salt.

3. An impregnated organoboron covalent organic network according to claim 1 or 2, wherein the salt is a salt of formula MX1, M being a metal cation selected from alkali metal cations and alkaline earth metal cations, preferably selected from Li + , N / A + , K + , Mg 2+ and that 2+ , advantageously is Li +, and X1 being an anion comprising at least one halogen, preferably is chosen from halide ions, the perchlorate anion ClO4- and the bis(trifluoromethanesulfonyl)imide anion.

4. Impregnated organoboron covalent organic network according to any one of claims 1 to 3, wherein the salt is lithium iodide.

5. Impregnated organoboron covalent organic network according to any one of claims 1 to 4, wherein the molar ratio between the molar quantity of alkali metal or alkaline earth metal and the molar quantity of boron is between 0.05 and 10, preferably between 0.1 and 5, preferably between 0.2 and 4, preferentially between 0.3 and 3.

6. Impregnated organoboron covalent organic network according to any one of the preceding claims, wherein the organoboron covalent organic network corresponds to the following formula (I): in which A is a mono- or polycyclic organoboron fragment, optionally substituted, Z is a mono- or polycyclic organic fragment, optionally substituted, and in which each AZ bond is a carbon-boron bond, or the organoboron covalent organic network corresponds to the following formula (II): in which A is a mono- or polycyclic organoboron fragment, optionally substituted, X is a mono- or polycyclic organic fragment, optionally substituted, and in which each AX bond is a carbon-boron bond, or the organoboron covalent organic network is a spiroborate and corresponds to the following formula (III): in which D is a mono- or polycyclic organic fragment, optionally substituted, and R is a linear organic fragment, optionally substituted, and M' + is a cation selected from metal, alkali metal or alkaline earth metal cations, such as Li + , N / A +, K + , That 2+ , Mg 2+ or Al 3+ 7. Impregnated organoboron covalent organic network according to claim 6, wherein the organoboron covalent organic network is of formula (I).

8. Impregnated organoboron covalent organic network according to claim 6 or 7, wherein fragment A is selected from a fragment of formula (A-1) and a fragment of formula (A-2) wherein E is a mono- or polycyclic, optionally substituted, preferably aromatic hydrocarbon moiety.

9. An impregnated organoboron covalent organic network according to any one of claims 6 to 8, wherein the moiety Z comprises one or more optionally substituted 6-membered aromatic hydrocarbon rings, and when it comprises several rings, each ring is independently fused with one or more of the other rings and / or separated from the other ring(s) by at least one chemical bond.

10. An impregnated organoboron covalent organic network according to any one of the preceding claims, wherein the organoboron covalent organic network is selected from COF-1, COF-5 and COF-10, preferably is COF-5. 11.A method for preparing an impregnated organoboron covalent network according to any one of claims 1 to 10, comprising the following steps: - a step of providing an organoboron covalent network, - a step of adding to the organoboron covalent network a salt chosen from alkali metal salts and alkaline earth metal salts, said salt being in solution in an organic solvent, and obtaining a mixture, - a step of stirring the mixture, and - a step of removing the organic solvent by drying the mixture, said drying being divided into at least a first drying step and a second drying step.

12. The method of claim 11, wherein the first drying step is carried out at a temperature between 15°C and 30°C, and the second drying step is carried out at a temperature between 40°C and 180°C. 13.Use of an impregnated organoboron covalent network according to any one of claims 1 to 10 as a solid electrolyte in an all-solid-state battery.

14. Use of an impregnated organoboron covalent network according to any one of claims 1 to 10 as an additive in an electrolyte composition.

15. Electrolyte composition, comprising an impregnated organoboron covalent network according to any one of claims 1 to 10.

16. Solid separator for an all-solid-state battery comprising an impregnated organoboron covalent network according to any one of claims 1 to 10.

17. Electrode for an all-solid-state battery comprising an impregnated organoboron covalent network according to any one of claims 1 to 10.

18. All-solid-state battery comprising an impregnated organoboron covalent network according to any one of claims 1 to 10.

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