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

Abstract

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

Description

[Technical Field]

[0001] The present invention relates to an organoboron covalent organic framework (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 the impregnated organoboron covalent organic framework. The present invention also relates to use of the impregnated organoboron covalent organic framework as a solid electrolyte in an all-solid-state battery, as well as an all-solid-state battery separator, an all-solid-state battery electrode, and an all-solid-state battery comprising the impregnated organoboron covalent organic framework. [Background technology]

[0002] "Traditional" lithium batteries have high energy density and are used in many everyday products (e.g., electric vehicles, portable electronic devices). Lithium batteries are based on the reversible exchange of lithium ions between a positive electrode and a negative electrode, which are separated by an ion-conducting electrolyte. Classically, the electrolyte is an organic solvent mixed with a lithium salt. However, this electrolyte has drawbacks such as toxicity, flammability, and potentially compromising the safety of the battery, e.g., due to the risk of explosion.

[0003] Both US2019 / 284212 and CN114094172 describe organoboron covalent organic frameworks impregnated with lithium salts and a significant amount of organic solvent, which can be used as electrolytes in batteries. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] US2019 / 284212 [Patent Document 2] CN114094172 Summary of the Invention [Problem to be solved by the invention]

[0005] There is a need to develop safer batteries that maintain or improve on the performance of known batteries, and in particular to develop batteries that have high ionic conductivity at operating temperatures.

[0006] Lithium polymer batteries are currently a promising alternative for battery safety, offering novel properties (e.g., flexibility) and reducing the use of precious resources. PEO technology is one example of this technology. However, while PEO technology has enabled the construction of highly efficient batteries, its performance is currently limited by its operating temperature (60°C) and the ability to recycle the electrolyte at the end of the battery's life.

[0007] Therefore, there is a need for new all-solid-state electrolyte materials.

[0008] In particular, there is a need for all-solid-state electrolyte materials with high ionic conductivity, especially over a wide range of operating temperatures, and it is believed that for applications as ionic electrolytes, these materials should potentially have the lowest electrical conductivity.

[0009] There is also a need for all-solid-state electrolyte materials that have better recycling capabilities than current electrolytes. [Means for solving the problem]

[0010] The inventors have now discovered, very surprisingly, that these aims can be achieved by means of a material based on a particular structure, more precisely on organoboron covalent organic frameworks impregnated with particularly selected salts, which, unlike the ionic electrolyte materials proposed in the prior art, does not contain organic solvents, an achievement not suggested in the prior art.

[0011] Therefore, the present invention relates to an organoboron covalent organic framework impregnated with at least one salt selected from alkali metal salts and alkaline earth metal salts.

[0012] More specifically, the present invention relates to an organoboron covalent organic framework impregnated with at least one salt selected from alkali metal salts and alkaline earth metal salts, the impregnated organoboron covalent organic framework being substantially free of organic solvents.

[0013] Covalent organic frameworks are known by the acronym COF.

[0014] Covalent organic frameworks are porous, crystalline, two- or three-dimensional materials prepared by periodically covalently bonding light elements (e.g., B, C, N, O). Covalent organic frameworks are therefore composed of periodically repeating elemental units.

[0015] Organoboron compounds, according to the present invention, are organic compounds that have at least one bond between a carbon atom and a boron atom.

[0016] The organoboron covalent organic framework according to the present invention is therefore a covalent organic framework comprising at least one boron atom in the element unit.

[0017] According to the present invention, "substantially free of organic solvents" means that the impregnated organoboron covalent organic framework contains less than 5% by weight, 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 of organic solvents, based on the total weight of the impregnated organoboron covalent organic framework. Advantageously, the impregnated organoboron covalent organic framework is completely free of organic solvents.

[0018] In the context of the present invention, the term organic "solvent" includes ionic liquids that possess all the properties necessary to identify a substance as an organic solvent, as known to those skilled in the art.

[0019] The organic solvent may be polar, such as acetone, ethyl acetate, acetonitrile, dimethylformamide, dimethoxyethane, dioxane, triethylamine, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-octylpyrrolidone, methanol, ethanol, isopropyl alcohol, diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyltetrahydrofuran, or 2-ethoxy-2-methylpropane.

[0020] The impregnated organoboron covalent organic framework according to the present invention is particularly substantially free of tetrahydrofuran. According to the present invention, "substantially free of tetrahydrofuran" means that the impregnated organoboron covalent organic framework contains less than 5% by weight, 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 of tetrahydrofuran, based on its total weight. Advantageously, the impregnated organoboron covalent organic framework is completely free of tetrahydrofuran.

[0021] The impregnated organoboron covalent organic framework according to the present invention is also substantially free of ionic liquid. According to the present invention, "substantially free of ionic liquid" means that the impregnated organoboron covalent organic framework contains less than 5% by weight, 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 of ionic liquid, based on its total weight. Advantageously, the impregnated organoboron covalent organic framework is completely free of ionic liquid.

[0022] Preferably, the impregnated organoboron covalent organic framework of the present invention is 50 ml 2 / g or more, preferably 250m 2 / g or more, preferably 500m 2 / g or more, especially 500m 2 The specific surface area of ​​the impregnated organoboron covalent organic framework of the present invention is preferably 50 to 3000 m2 / g, preferably between 400 and 1600m 2 / g, especially between 500 and 1600m 2 / g.

[0023] The specific surface area can be determined by nitrogen adsorption: the nitrogen gas adsorption isotherm is analyzed using a Micromeritics Porosimetry Analyzer ASAP 2020. The measurement is carried out at 77 K (liquid nitrogen bath) on a degassed and activated 300 mg sample.

[0024] Preferably, the impregnated organoboron covalent organic framework according to the present invention has a pore diameter of 1.0 nm or more, preferably 1.5 nm or more, preferably 2.0 nm or more, preferably between 1.0 and 5.0 nm, preferably between 2.0 and 3.0 nm.

[0025] The pore diameter can be determined from the nitrogen adsorption isotherm, for example, at 77K according to the BJH (Barret-Joyner-Halenda) method.

[0026] Advantageously, the impregnated organoboron covalent organic frameworks of the present invention decompose in the presence of water, and when used as battery electrolytes, this instability in the presence of water allows for much easier recycling than prior art electrolytes.

[0027] Organoboron covalent organic framework The covalent organic framework is preferably two-dimensional or three-dimensional, preferentially two-dimensional.

[0028] The organoboron covalent organic framework is preferably represented by the following formula (I): [ka] wherein A is an optionally substituted monocyclic or polycyclic organoboron moiety, Z is an optionally substituted monocyclic or polycyclic organic moiety, and each A-Z bond is a carbon-boron bond. or having the following formula (II): [ka] wherein A is an optionally substituted monocyclic or polycyclic organoboron moiety, X is an optionally substituted monocyclic or polycyclic organic moiety, and each AX bond is a carbon-boron bond. or a spiroborate salt having the following formula (III): [ka] wherein D is an optionally substituted monocyclic or polycyclic organic moiety, R is an optionally substituted linear organic moiety, and M' + Li + , Na + , K. + , Ca 2+ , Mg 2+ , or Al 3+ The cation is selected from metal, alkali metal, or alkaline earth metal cations such as It has.

[0029] "Optionally substituted" preferably means in the context of the entire application that it is optionally substituted with at least one C1 to C6, preferably C1 to C3, alkyl group, which may contain oxygen atoms inserted therein and / or anionic groups, such as carboxylic, sulfonic or phosphate groups, or halogenated groups, such as trifluoromethanesulfonimide groups.

[0030] The organoboron covalent organic frameworks of formulas (I) and (III) are two-dimensional, and the organoboron covalent organic frameworks of formula (II) are three-dimensional.

[0031] The organoboron covalent organic framework is preferably an organoboron covalent organic framework of formula (I).

[0032] In formula (I), each AZ bond is preferably a bond between a boron atom of moiety A and a carbon atom of moiety Z.

[0033] In formula (II), each AX bond is preferably a bond between a boron atom of moiety A and a carbon atom of moiety X.

[0034] The organoboron covalent organic framework preferably consists of carbon, hydrogen, boron, oxygen atoms, and optionally silicon.

[0035] According to the present invention, a monocyclic compound means a compound containing one ring, saturated or unsaturated, and optionally containing one or more heteroatoms such as N or O.

[0036] According to the present invention, a polycyclic compound means a compound comprising at least two rings, each ring being independently saturated or unsaturated, fused (sharing at least two atoms) with one or more other rings, and / or separated from the other rings by at least one chemical bond, and optionally containing one or more heteroatoms such as N or O.

[0037] In formula (I), each A-Z chemical bond preferably forms a boronic ester functional group, and each A-Z bond preferably corresponds to a bond between a carbon of moiety Z and a boron of a B(O) unit of moiety A.

[0038] In formula (II), each AX chemical bond preferably forms a boronic ester functional group, and each AX bond preferably corresponds to a bond between a carbon of moiety X and a boron of a B(O) unit of moiety A.

[0039] In formula (I) or (II), the moiety A is preferably a moiety of formula (A-1): [ka] and the portion of formula (A-2): [ka] wherein E is a monocyclic or polycyclic, optionally substituted, preferably aromatic, hydrocarbon moiety. is selected from.

[0040] E is preferably a moiety comprising one or more six-membered hydrocarbon rings, each of which is independently saturated or contains at least one unsaturation, is preferably aromatic, and is optionally substituted. E preferably comprises at least two six-membered hydrocarbon aromatic rings, each of which is optionally substituted and each ring is independently fused (sharing two atoms) to one or more other rings and / or separated from the other rings by at least one chemical bond. More preferably, E comprises at least three six-membered hydrocarbon aromatic rings, each of which is optionally substituted and each ring is fused to at least one other ring, preferably exactly one other ring. Advantageously, E comprises four six-membered hydrocarbon aromatic rings, preferably consisting of four six-membered hydrocarbon aromatic rings, each of which is fused to at least one other ring, preferably exactly one other ring.

[0041] Advantageously, the moiety A is a moiety of formula (A-1): [ka] and the portion of formula (A-21): [ka] is selected from.

[0042] In formula (I), Z is preferably a moiety comprising one or more six-membered hydrocarbon rings, each ring independently saturated or containing at least one unsaturation, preferably aromatic, and optionally substituted. Z preferably comprises one or more optionally substituted six-membered hydrocarbon aromatic rings, and when Z comprises multiple rings, each ring is independently fused (shares two atoms) with one or more other rings and / or separated from the other rings by at least one chemical bond.

[0043] More preferably, Z comprises, and preferably consists of, one to six, preferably one to four, preferably one, two, or three six-membered hydrocarbon aromatic rings, each of which is optionally and independently substituted, and when Z comprises multiple rings, each ring is separated from the other rings by at least one, preferably one, two, or three, chemical bond, forming a linear series of rings, each ring preferably separated from the other rings by exactly one carbon-carbon chemical bond or by three chemical bonds in a linear series, the second chemical bond being a carbon-carbon double bond or a carbon-nitrogen double bond.

[0044] Advantageously, the moiety Z is a moiety of formula (Z-1): [ka] Part of formula (Z-2): [ka] Part of formula (Z-3): [ka] and the moiety of formula (Z-3'): [ka] is selected from.

[0045] In formula (II), X is preferably a moiety containing one or more six-membered hydrocarbon rings, wherein each ring is independently saturated or contains at least one unsaturation, is preferably aromatic, and is optionally substituted. X preferably contains at least two, preferably two to four, optionally substituted six-membered hydrocarbon aromatic rings, wherein each six-membered hydrocarbon aromatic ring is separated from the other rings by at least one chemical bond, and preferably all rings are linked to the same tetravalent atom, preferably the same carbon or silicon atom. More preferably, X contains four six-membered hydrocarbon aromatic rings, preferably consisting of four six-membered hydrocarbon aromatic rings, wherein each six-membered hydrocarbon aromatic ring is linked to the same tetravalent atom, preferably the same carbon or silicon atom.

[0046] Advantageously, the moiety X has the formula (X-1): [ka] (wherein G is a carbon atom or a silicon atom).

[0047] In formula (III), D is preferably a moiety comprising one or more five- or six-membered hydrocarbon rings, wherein each ring is independently saturated or contains at least one unsaturation and is optionally substituted. D preferably comprises two or three five- or six-membered rings, each ring independently fused (sharing two atoms) with one or more other rings.

[0048] Advantageously, D is of formula (G-1): [ka] This is the part.

[0049] In formula (III), R is preferably a linear hydrocarbon moiety, saturated or containing at least one unsaturation, containing from 1 to 6, preferably from 2 to 4, advantageously 2 carbon atoms. Advantageously, R is a -C≡C- group.

[0050] The organoboron covalent organic framework is preferably COF-1, COF-5, COF-10, COF of formula (I) (wherein A is (A-1) and Z is (Z-3)), COF of formula (I) (wherein A is (A-1) and Z is (Z-3')), COF of formula (I) (wherein A is (A-21) and Z is (Z-3)), COF of formula (I) (wherein A is (A-21) and Z is (Z-3')), COF-102 (wherein A COF-103 (wherein A is (A-1), X is (X-1), and G is silicon, formula (II)), COF-105 (wherein A is (A-21), X is (X-1), and G is silicon, formula (II)), COF-108 (wherein A is (A-21), X is (X-1), and G is carbon, formula (II)), and the following formula (III-A): [ka] (In the formula, M' + Li + , Na + , K. + , Ca 2+ , Mg 2+ , or Al 3+ The cation is selected from metal, alkali metal, and alkaline earth metal cations such as The spiroborate COFs are selected from the group consisting of:

[0051] The structures of organoboron covalent organic frameworks COF-1, COF-5, COF-10, COF-102, COF-103, COF-105, and COF-108 are well known to those skilled in the art.

[0052] More preferably, the organoboron covalent organic framework is selected from COF-1, COF-5, and COF-10, preferably COF-5.

[0053] COF-1 is an organoboron covalent organic framework of formula (I), where A is formula (A-1) and Z is formula (Z-1), as defined above.

[0054] COF-5 is an organoboron covalent organic framework of formula (I), where A is formula (A-21) and Z is formula (Z-1), as defined above.

[0055] COF-10 is an organoboron covalent organic framework of formula (I), where A is formula (A-21) and Z is formula (Z-2), as defined above.

[0056] salt The impregnated organoboron covalent organic framework according to the present invention comprises at least one salt.

[0057] The salts are selected from alkali metal salts and alkaline earth metal salts, and are preferably alkali metal salts, and preferably lithium salts.

[0058] Preferably, the salt is of the formula MX1, where M is a metal cation selected from alkali metal cations and alkaline earth metal cations, and X1 is an anion containing at least one halogen.

[0059] Preferably, M is Li + , Na + , K. + , Mg 2+ , and Ca 2+ and preferably Li + is.

[0060] Preferably, X1 is a halide ion, preferably Br - or I - , advantageously I -, perchlorate anion ClO4 - , bis(trifluoromethanesulfonyl)imide anion (known as TFSI), bis(fluorosulfonyl)imide anion (known as FSI), hexafluorophosphate anion PF6 - , tetrafluoroborate anion BF4 - , bis(pentafluoroethanesulfonyl)imide anion (known as BETI), C1 to C4 fluoroalkyl-4,5-dicyano-imidazolate anions, such as trifluoromethyl-4,5-dicyano-imidazolate anion or pentafluoroethyl-4,5-dicyano-imidazolate anion, more preferably halide ions, preferably Br - or I - , more preferably I - , perchlorate anion ClO4 - and bis(trifluoromethanesulfonyl)imide anion. Advantageously, X1 is selected from I - It is an ion.

[0061] The salt is preferably lithium iodide.

[0062] According to another embodiment, the salt is an ammonium ion salt, preferably a quaternary ammonium, preferably a C1 to C4 tetraalkylammonium salt such as a tetramethylammonium salt, or a phosphonium ion salt, preferably a quaternary phosphonium salt, preferably a C1 to C4 tetraalkylphosphonium salt such as a tetramethylphosphonium salt. According to this embodiment, the anion of the salt is preferably a halide ion, preferably an iodide ion.

[0063] The impregnated organoboron covalent organic framework according to the present invention preferably has a molar ratio of the molar amount of alkali metal or alkaline earth metal to the total molar amount of boron in the impregnated organoboron covalent organic framework of between 0.05 and 10, preferably 0.1 and 5, preferably 0.2 and 4, preferably 0.3 and 3.

[0064] The molar amount of the alkali metal or alkaline earth metal, and the molar amount of boron are defined relative to the total molar amount of the impregnated organoboron covalent organic framework; that is, the molar amount of boron taken into account in calculating the ratio includes the boron contained in the organoboron covalent organic framework and the boron that may be contained in the salt.

[0065] The present invention also relates to a method for producing a method for manufacturing a semiconductor device comprising the steps of: providing an organoboron covalent structure; adding a solution of a salt selected from alkali metal salts and alkaline earth metal salts in an organic solvent to the organoboron covalent structure to obtain a mixture; stirring the mixture; and a step of totally or substantially totally removing the organic solvent by drying the mixture, which drying is divided into at least a first drying step and a second drying step; The present invention relates to a method for preparing an impregnated organoboron covalent framework comprising:

[0066] The organoboron covalent framework and salt are preferably as defined above for the impregnated organoboron covalent organic framework.

[0067] The stirring step is preferably carried out for a period of at least 120 hours, preferably at least 144 hours, preferably at least 168 hours, preferably between 120 and 340 hours.

[0068] The step of removing the organic solvent is preferably carried out directly on the mixture, in particular without prior mechanical treatment, which is preferably also not carried out between the first and second drying steps.

[0069] At least one of the first drying step and the second drying step is preferably carried out at a temperature 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.

[0070] The first drying step is preferably carried out at a temperature between 15°C and 30°C, preferably about 25°C. The first drying step is preferably carried out under reduced pressure. The first drying step is preferably carried out under an inert atmosphere. The first drying step is preferably carried out for a period of 5 to 36 hours, preferably 6 to 24 hours, preferably 10 to 20 hours.

[0071] The second drying step is preferably carried out at a temperature between 40°C and 180°C, preferably between 50 and 150°C, preferably between 60 and 130°C. The second drying step is preferably carried out under reduced pressure. The second drying step is preferably carried out under an inert atmosphere. The second drying step is preferably carried out for a period of 2 to 12 hours, preferably between 4 and 10 hours, preferably between 5 and 7 hours.

[0072] The drying preferably further comprises a third drying step.

[0073] The third drying step is preferably carried out at a temperature between 80°C and 180°C, preferably between 100 and 150°C, preferably between 110°C and 130°C. The third drying step is preferably carried out under reduced pressure. The third drying step is preferably carried out under an inert atmosphere. The third drying step is preferably carried out for a period of 8 to 48 hours, preferably between 10 and 36 hours, preferably between 12 and 20 hours. According to this embodiment, the second drying step is preferably carried out at a temperature between 30 and 100°C, preferably between 40 and 90°C, preferably between 50 and 80°C, preferably between 60 and 70°C. The second drying step is preferably carried out under reduced pressure. The second drying step is preferably carried out under an inert atmosphere. The second drying step is preferably carried out for a period of 2 to 12 hours, preferably between 4 and 10 hours, preferably between 5 and 7 hours.

[0074] "Under reduced pressure" means under a pressure of 1 to 50 mbar, preferably 3 to 30 mbar, preferably 5 to 15 mbar.

[0075] "Under an inert atmosphere" preferably means an atmosphere containing 0.1 to 10 ppm O2 and / or 0.1 to 10 ppm water.

[0076] The organic solvent is preferably polar.

[0077] The polar solvent is preferably not tetrahydrofuran.

[0078] The organic solvent preferably has a boiling point at atmospheric pressure of 65°C or less, preferably between 30 and 60°C, and / or a vapor pressure at 20°C of more than 20 kPa, preferably between 23 and 40 kPa.

[0079] The organic solvent is selected, for example, from acetone, ethyl acetate, acetonitrile, dimethoxyethane, dioxane, N,N-dimethylacetamide, N-ethyl-2-pyrrolidone, and N-octylpyrrolidone, methanol, ethanol, isopropyl alcohol, diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl-tetrahydrofuran, or 2-ethoxy-2-methylpropane, and is advantageously acetone.

[0080] The present invention also relates to the use of the impregnated organoboron covalent framework according to the present invention as a solid electrolyte in an all-solid-state battery.

[0081] The impregnated organoboron covalent frameworks are preferably used as separator and / or electrolyte materials in electrodes of all-solid-state batteries.

[0082] The all-solid-state battery can be a lithium ion type, a lithium primary (non-rechargeable), a lithium metal (rechargeable or non-rechargeable), a dual ion double electrolyte, a sodium ion, a potassium ion, a magnesium ion, or a calcium ion, or a sodium metal, preferably a lithium ion, a primary lithium, and a lithium metal type battery.

[0083] When used in a separator, the impregnated organoboron covalent structure can be used alone or in combination with one or more additional compounds, such as a binder, preferably a polymeric binder.

[0084] When used as an electrolyte material in an electrode of an all-solid-state battery, the impregnated organoboron covalent framework may be used in combination with one or more additional conventionally used compounds, such as a positive or negative electrode active material, and optionally, a binder and / or a conductive additive.

[0085] The conductive additives may be selected from carbon fibers, carbon black, carbon nanotubes, graphite, graphene, acetylene black, and analogs thereof, metal particles such as silver or copper particles, conductive polymers such as poly-p-phenylene, poly(3,4-ethylenedioxythiophene) (PEDOT), polyaniline (PANI), or polypyrrole, and charge transfer complexes such as those of the tetrathiofulvalenium-tetracyanoquinodimethane (TTF-TCNQ) type.

[0086] The binder 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 latexes of the styrene-butadiene rubber type.

[0087] An electrode can be either a positive or negative electrode. By "negative electrode" we mean the electrode that functions as an anode when the battery is discharging, and by "positive electrode" we mean the electrode that functions as a cathode when the battery is discharging.

[0088] The positive electrode active material is not particularly limited, - A material that can reversibly insert lithium ions, Li x oxides such as MO2 (0.5≦x≦3) (wherein M represents at least one metal element selected from the group consisting of Ni, Co, Mn, Fe, Cr, Ti, Cu, V, Al, and Mg), and Lix V2O5 (0 ≦ x ≦ 5) or Li x Vanadates such as V3O8 (1 ≦ x ≦ 3), phosphates such as LiFePO4, Li3Fe2(PO4)3, LiV2(PO4)3, silicates such as Li2FeSiO4, borates such as LiFeBO3, and sulfates such as LiFeSO4F, Li2Fe2(SO4)3, and materials that can be selected therefrom - A material capable of reversibly inserting lithium ions, Li 1+y+z / 3 Ti 2-z / 3 O4 (0 < z < 1, 0 < y < 1), Li 4+z’ Ti5O 12 (0 < z’ < 3) Oxides of the formula, carbon, carbon compounds produced by thermal decomposition of organic materials, and materials selected from organic carboxylates such as terephthalates - Organic electrode materials such as benzoquinone and its derivatives, 7,7,8,8,-tetracyano-p-quinodimethane and its derivatives, oxymate, sulfonimide, perylene diimide, and dianhydride can be selected from.

[0089] The negative electrode active material is not particularly limited and can be selected from carbon materials, particularly hard carbon, soft carbon, carbon nanofibers or carbon felt, antimony, tin, and phosphorus.

[0090] The present invention also relates to the use of the impregnated organic boron covalent structure according to the present invention as an additive to an electrolyte composition.

[0091] The electrolyte composition is as follows: - A salt as defined above, for example LiI, which is a solution of an alkali metal salt or an alkaline earth metal salt in a solvent conventionally used in the electrolyte composition, for example N-methylpyrrolidone (NMP) or acetone, or - Polymers containing oxygen such as polyethylene oxide, PEO (5 - 100000), polymers containing an immobilized (trifluoromethylsulfonyl) imide (TFSI) moiety such as poly(4-styrenesulfonyl(trifluoromethylsulfonyl)imide) (PSTFSI), or - Sulfide-type ceramic materials such as argyrogenite may include:

[0092] The inclusion of the impregnated organoboron covalent structure according to the present invention in an electrolyte composition advantageously improves the electrochemical performance of the electrolyte composition. For example, when the impregnated organoboron covalent structure is used together with a conductive polymer, cooperation between the impregnated organoboron covalent structure and the conductive polymer is observed, particularly in terms of electrical conductivity.

[0093] Thus, the present invention also relates to an electrolyte composition comprising an impregnated organoboron covalent organic framework according to the present invention.

[0094] The electrolyte composition may further comprise, in addition to the impregnated organoboron covalent organic framework, a solution of an alkali metal salt or alkaline earth metal salt, an oxygen-containing polymer, or a ceramic material as defined above with respect to the use as an additive of the impregnated organoboron covalent framework according to the present invention.

[0095] The electrolyte composition preferably comprises at least 0.2 wt. % of the impregnated organoboron covalent organic framework, preferably an amount of 0.5 wt. % or more, preferably an amount between 0.5 and 50 wt. %, based on the total weight of the electrolyte composition.

[0096] Therefore, the present invention also relates to a solid separator for an all-solid-state battery comprising an impregnated organoboron covalent structure according to the present invention.

[0097] The separator according to the present invention is as defined above.

[0098] Therefore, the present invention also relates to an electrode for an all-solid-state battery comprising an impregnated organoboron covalent framework according to the present invention.

[0099] The electrode can be positive or negative.

[0100] Positive electrodes comprising the impregnated organoboron covalent frameworks according to the present invention further comprise an active positive electrode material and, optionally, a binder and / or a conductive additive, these components being as defined above.

[0101] A negative electrode comprising an impregnated organoboron covalent framework according to the present invention further comprises an active negative electrode material and, optionally, a binder and / or a conductive additive, these components being as defined above.

[0102] The positive or negative electrode may further include a current collector, for example, an aluminum or copper strip, or a conductive carbon layer, or a polymer layer such as poly(3,4-ethylenedioxythiophene).

[0103] The present invention further relates to an all-solid-state battery comprising the impregnated organoboron covalent framework according to the present invention.

[0104] The all-solid-state battery can be a lithium ion type, lithium primary (non-rechargeable), lithium metal (rechargeable or non-rechargeable), dual ion double electrolyte, sodium ion, potassium ion, magnesium ion, calcium ion, or sodium metal, preferably a lithium ion, primary lithium, and lithium metal type battery.

[0105] The all-solid-state battery includes a positive electrode, a negative electrode, and a separator.

[0106] As explained above, the impregnated organoboron covalent structures according to the present invention may be present in the separator and / or the positive electrode and / or the negative electrode of the battery, each of these elements being individually defined above.

[0107] The invention will now be described by way of non-limiting examples. [Brief explanation of the drawings]

[0108] Figure 1 shows a set of FT-IR spectra (500 to 1750 cm -1) and compares, from top to bottom, ABDB, COF-5, lithium salts, and COF-5 impregnated with the lithium salts (Li / B molar ratio is 1). The lithium salts are a) LiClO4, b) LiBr, c) LiTFSI, and d) LiI.

[0109] Figure 2 shows a set of FT-IR spectra (500 to 4000 cm -1 ) and compares, from top to bottom, ABDB, COF-5, lithium salts, and COF-5 impregnated with the lithium salts (Li / B molar ratio is 1). The lithium salts are a) LiClO4, b) LiBr, c) LiTFSI, and d) LiI.

[0110] FIG. 3 is a set of FT-IR spectra comparing COF-1 and COF-1 impregnated with LiI (Li / B ratio is 2).

[0111] FIG. 4 is a set of FT-IR spectra comparing COF-10 and COF-10 impregnated with LiI (Li / B ratio is 2).

[0112] FIG. 5 is a set of EIS spectra as a function of Li / B ratio for COF-5-based impregnated organoboron covalent frameworks, where the lithium salt is a) LiClO (left) or LiTFSI (right).

[0113] FIG. 6 is a set of EIS spectra of organoboron covalent frameworks based on COF-1 or COF-5 impregnated with LiI (Li / B molar ratio of 2) and, for comparison, LiI alone.

[0114] FIG. 7 is a set of EIS spectra of organoboron covalent frameworks based on COF-10 or COF-5 impregnated with LiI (Li / B molar ratio of 2) and, for comparison, LiI alone.

[0115] FIG. 8 shows two galvanostatic cycling curves of batteries containing a lithium salt-based solid electrolyte in the separator, either the impregnated COF COF-5@LiI (left) or LiI alone (right).

[0116] FIG. 9 is a galvanostatic cycling curve of a Li-metal / organic polymer battery according to Example 4 (anode is Li-TCNQ).

[0117] FIG. 10 is the galvanostatic cycling curves of the Li-metal / organic COF-5@LiI battery (anode is perylene diimide) according to Example 4.

[0118] Figure 11 shows the specific surface area of ​​2068 m 2 / g of COF-5 organoboron covalent framework (COF-5 h), and a specific surface area of ​​405 m 2 1 shows the Fourier transform infrared (FT-IR) spectra obtained for COF-5 organoboron covalent framework (COF-5 I) at 1000 nm / g, respectively.

[0119] FIG. 12 shows the results of electrochemical impedance spectroscopy of a 405 m2 SiO2 nanoparticle with a specific surface area of ​​405 m2 at different temperatures (20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, and 100°C). 2 1 shows the spectrum of LiI-impregnated COF-5 organoboron covalent framework at 1000 nm / g. DETAILED DESCRIPTION OF THE INVENTION

[0120] Methods for Analyzing Organoboron Covalent Structures and Impregnated Organoboron Covalent Structures According to the Present Invention Infrared (IR) spectroscopy Infrared spectra were measured on a Shimadzu 8400S FTIR spectrometer using an attenuated total reflectance analytical accessory (transmission mode - KBr). -1 From 500 cm -1 was measured between

[0121] Atomic absorption spectrometry Measurement of the lithium level in the impregnated organoboron covalent framework was carried out using a Perkin Elmer Analyst 300 spectrometer at a wavelength of 670.8 nm. A neon-filled hollow cathode (lithium) lamp was used as the light source, and a flame generated by a mixture of air and acetylene was used for atomization. 1 mol / L Li + Direct calibration was performed using three solutions of 1, 2, and 3 ppm concentration prepared using a commercial standard solution of 1 ppm Li. + The samples were prepared to a concentration of 0.01g and subsequently analyzed as unknown concentrations. The absorbance values ​​obtained were compared with a previously prepared calibration curve to obtain the actual concentration of Li+ and, accordingly, the lithium level of the compound. Each sample was analyzed in triplicate to verify the detected lithium levels.

[0122] NMR The spectrometer used is a BRUKER AVANCE III HD 500 MHz SB equipped with a CP_MAS solid probe and an Ultra Shield magnet of 11.7 T. The sample is loaded into a 4 mm ZrO2 rotor. Using cross polarization and magic angle spinning (CP-MAS), 13 C. 11 B, and 7 Li NMR spectra were measured at a spinning rate of 15 kHz. 13 The chemical shifts of C were referenced to hexamethylbenzene at 17.3 ppm as the standard.

[0123] BET N2 gas adsorption isotherm analysis was performed using a Micromeritics porosimetry analyzer ASAP 2020. Measurements were performed at 77 K (liquid nitrogen bath) on 300 mg degassed and activated samples before and after impregnation with lithium salts.

[0124] Example 1: Preparation of different organoboron covalent frameworks A variety of organoboron covalent frameworks were prepared according to the following protocol.

[0125] Synthesis of COF-5 In a 500 mL flask, 784 mg of hexahydroxytriphenylene (HHTP, supplier: TCI) and 602 mg of benzenediboronic acid (("ABDB"), supplier: Sigma Aldrich, Merck), previously ground and dried overnight at room temperature under vacuum, were added.

[0126] [ka]

[0127] [ka]

[0128] To the mixture was added 1.47 mL of methanol, followed by 301 mL of a ¼-volume mesitylene / anhydrous 1,4-dioxane mixture. The flask was then placed in an ultrasonic bath for 10 minutes and then heated at 90°C with vigorous stirring (≦500 rpm) for 7 days. The resulting greenish-gray precipitate was filtered and washed with anhydrous acetone and toluene. The powder was then dried in a programmable vacuum tube oven (Buchi) under vacuum for 6 hours, then at 70°C for 6 hours, and finally at 120°C for 12 hours.

[0129] IR and NMR analysis of the obtained product gave the following results: IR (KBr pellet) (cm -1 ):1522;1491;1450ν(C=C);1350ν(BO);1324ν(BO);1240ν(CO);1161ν(CH);1077ν(CH);1026ν(BC);849ν(CH);832;657;612 NMR CP MAS 13 C δ in ppm:146.72(CO);132.8(CB);123.85(C=C);102.98(CHAr ) NMR CP MAS 11 B δ in ppm: 21.07 (BO), 13.83 (BC)

[0130] Synthesis of COF-1 200 mg of benzene-1,4-diboronic acid (Sigma Aldrich, Merck), previously hand-ground and dried overnight under vacuum at room temperature, was added to a dried flask, and 40 mL of a 1:1 volume mixture of methylene and 1,4-dioxane was added under an inert atmosphere (argon). The mixture was placed in an ultrasonic bath for 5 minutes, then bubbled for 30 minutes, and finally heated to 80°C for 72 hours. The white powder obtained by centrifugation was washed with anhydrous acetone and then dried in a BUCHI oven at 65°C for 6 hours and then at 120°C for 6 hours (82% yield).

[0131] IR (KBr pellet) (cm -1 ):1509ν(C=C);1398ν(BO);1339ν(BO);1301ν(CC);1107ν(CH);1019ν(CH);711ν(B3O3); NMR CP MAS 13 C δ in ppm: 133; 127 NMR CP MAS 11 B δ in ppm: 31.82; 32.89

[0132] Synthesis of COF-10 112 mg of HHTP (TCI), 86 mg of biphenyldiboronic acid ABPD (Sigma Aldrich, Merck), previously hand-ground and dried overnight at room temperature under vacuum, and 0.21 mL of methanol were added to the flask.

[0133] [ka]

[0134] The mixture was dissolved in 43 mL of a 1:4 mesitylene:dioxane mixture, then placed in an ultrasonic bath for 1 minute, then heated to 90°C with vigorous stirring for 7 days. The solid was isolated by filtration and quickly washed with toluene, then anhydrous acetone. The solid was dried under vacuum at 120°C overnight (79% yield).

[0135] 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 NMR CP MAS 11 B δ in ppm:1.09.

[0136] 1.4. Synthesis of imine-boroxine-COF-1 A 100 mL flask was charged with 300 mg of 4-formylphenylboronic acid (FPBA) and 108 mg of 1,4-phenylenediamine (PDA) in a 1 / 3 volumetric solution of 1,4-dioxane / mesitylene (40 mL). The mixture was placed in an ultrasonic bath for 10 minutes and then flash-frozen at 77 K. The mixture was then degassed under vacuum until thawed. This procedure was repeated three times. The reaction mixture was then heated to 120 °C for three days. The orange-brown precipitate was collected by filtration and washed with anhydrous acetone. The product was then soaked in dichloromethane for three days, during which the activation solvent was decanted and replenished four times with fresh water. The resulting orange-brown precipitate was dried at room temperature and then at 100 °C under vacuum overnight (78% yield).

[0137] IR (KBr pellet) (cm -1 ):1656ν(C=O);1626ν(C=N);1497ν(CH);1441;1315ν(BO);1216ν(BC);1019ν(CH);1011;870;710ν(B3O3);631;532;504;474;442 NMR CP MAS13 C δ in ppm: 159 (C=N); 150 (C Ar -N);139 (C Ar -C=);127(CB);116(C Ar -H).

[0138] 1.5. Synthesis of imine-boronate-COF-2 A 100 mL solution of 270 mg of 4-formylphenylboronic acid, 105 mg of 1,4-phenylenediamine, and 195 mg of hexahydroxytriphenylene in a 1 / 3 volume ratio of 1,4-dioxane / mesitylene (40 mL) was added to a 100 mL flask. The flask was placed in an ultrasonic bath for 10 minutes and then quickly frozen at 77 K. The mixture was then degassed under vacuum until thawed. This procedure was repeated three times. The reaction mixture was then heated to 120 °C for three days. The green precipitate was collected by filtration and washed with anhydrous acetone. The product was then soaked in dichloromethane for three days, during which the activation solvent was decanted and replenished four times with fresh water. The resulting green-brown precipitate was dried at room temperature and then at 100 °C under vacuum overnight (79% yield).

[0139] IR (KBr pellet) (cm -1 ):1688ν(C=O);1608ν(C=N);1491ν(CH);1445;1353ν(BO);1325ν(BO);1241ν(CO);1160;1062ν(BC);1015;976;856;845;728 NMR CP MAS 13 C δ in 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).

[0140] 1.6. Imine-boroxine-COF-1 SO 3 Synthesis of Li A solution of 300 mg of FPBA (Sigma-Aldrich, Merck) and 195.22 mg of lithium 1,4-phenylenediamine-2-sulfonate (PaSO3Li) in 40 mL of 1,4-dioxane / mesitylene (1 / 3 volume ratio) was added to a 100 mL flask. The mixture was placed in an ultrasonic bath for 10 minutes and then frozen at 77 K. The mixture was then degassed under vacuum until thawed. This procedure was repeated three times. The reaction mixture was then heated to 120 °C for three days. The orange precipitate was collected by filtration and washed with anhydrous acetone. The product was then soaked in DCM for three days, during which the activation solvent was decanted and replenished four times with fresh water. The resulting orange-brown precipitate was dried at room temperature and then at 100 °C under vacuum overnight (62% yield).

[0141] IR (KBr pellet) (cm -1 ):1656ν(C=O);1626ν(C=N);1497ν(CH);1441;1315ν(BO);1155ν(S=O);1019;1011;870ν(SO);833ν(SO);711ν(B3O3);631;532;504;474;442 NMR CP MAS 13 C δ in ppm:159 (C=N);146 (CN);139 (CC Ar );127 (CB);117 (C=CH).

[0142] 1.7. Synthesis of Imine-Boronate-COF-2 SO3Li A 100 mL flask was charged with 451 mg of FPBA, 169 mg of lithium 1,4-phenylenediamine-2-sulfonate, and 195 mg of hexahydroxytriphenylene in 40 mL of 1,4-dioxane / mesitylene (1 / 3 volume ratio). The mixture was placed in an ultrasonic bath for 10 minutes and then frozen at 77 K. The mixture was then degassed under vacuum until thawed. This procedure was repeated three times. The reaction mixture was then heated to 120 °C for three days. The brown precipitate was collected by filtration and washed with anhydrous acetone. The product was then soaked in DCM for three days, during which the activation solvent was decanted and replenished four times with fresh water. The resulting brown precipitate was dried at room temperature and then at 100 °C under vacuum overnight (70% yield).

[0143] IR (KBr pellet) (cm -1 ):1602ν(C=N);1491ν(CH);1445;1354ν(BO);1334ν(BO);1241ν(CO);1160ν(S=O);1106;1062ν(BC);1015;981;833ν(SO);728;697;652;610 NMR CP MAS 13 C δ in ppm: 157 (C=N); 146 (C Ar -N);139 (C Ar -C=);132 (C Ar -H);124 (C Ar =C Ar );103.98 (C Ar -H).

[0144] Example 2: Preparation of different impregnated organoboron covalent frameworks according to the present invention 100 mg of the dried and activated COF was placed in a pill container. The pill container was vacuum sealed, and then 6 mL of a solution of different lithium salts prepared in anhydrous acetone was added. The identity and amount of the lithium salts are summarized in Table 1 below. The mixture was stirred for 7 days. After acetone was evaporated at room temperature under an inert atmosphere, the different impregnated COF samples were dried under vacuum (approximately 10 mbar) for 4 hours at room temperature, then at 65°C for 6 hours, and finally at 120°C for 14 hours.

[0145] [Table 1]

[0146] The Li / B molar ratio was determined by atomic absorption spectroscopy of the impregnated organoboron covalent framework and corresponds to the Li / B ratio of the introduced reagent.

[0147] Example 3: Identification of Impregnated Organoboron Covalent Frameworks According to the Invention The impregnated organoboron covalent frameworks of Example 2 were characterized by IR spectroscopy, comparing the spectra of each COF and the corresponding lithium salt (see Figures 1 to 4).

[0148] The different impregnated COFs were also analyzed by NMR spectroscopy. The results of the two analytical techniques are summarized below:

[0149] -COF-5@LiClO4: IR (KBr pellet) (cm -1 ):1522:1494;1448;1395;1348ν(BO);1329ν(BO);1243ν(CO);1145ν(Cl-O);1110ν(Cl-O);1080ν(BC);1018;853;832;655;636;626 NMR CP MAS 13 C δ in ppm:146.72 (CO);133.02 (C Ar -B);123.85 (C Ar =C Ar );103.08 (C Ar -H) NMR CP MORE 11 B δ in ppm: 21.38;

[0150] ‐COF-5@LiTFSI: IR(KBrBark)(cm -1 ):1521;1492;1450;1349ν(BO);1322ν(BO);1243ν(CO);1200ν(CF);1162ν(CF);1133;1075ν(BC);1019;851;832;657;577 NMR CP MORE 13 Cδ in ppm: 146.60 (CO); 133 (C Ar -B);127.86;123.85;123.79 (C=C);102.98 (CH Ar ) NMR CP MORE 11 B δ in ppm: 21.69;

[0151] ‐COF-5@LiI: . IR(KBrBark)(cm -1 ):1523;1491;1449;1350ν(BO);1322ν(BO);1240ν(CO);1159;1077ν(BC);1019;848;832;655;613 NMR CP MORE 13 C δ in ppm: 146.62 (CO); 133.8 (CB); 123.76 (C=C); 102.88 (CH). Ar ) NMR CP MORE 11 B δ in ppm: 20.64;7.01 NMR CP MORE 7 Liδ in ppm:0.32;-4.03 (LiI) NMR CP MORE 127 I δ in ppm:408

[0152] ‑COF-5@LiBr: IR(KBrBark)(cm -1):1523;1491;1451;1350ν(BO);1324ν(BO);1240ν(CO);1159;1077ν(BC);1021;848;832;657;611

[0153] -Imine-boroxine-COF-1@LiI: IR (KBr pellet) (cm -1 ):1653ν(C=O);1622ν(C=N);1487ν(CH);1441;1315ν(BO);1216ν(BC);1019ν(CH);1011;870;710ν(B3O3);631;533; NMR CP MAS 13 C δ in ppm:

[0154] 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).

[0155] N2 gas adsorption isotherm analysis was performed on several of the impregnated organoboron covalent frameworks of Example 2.

[0156] From these curves, the m of each impregnation COF 2 The specific surface areas expressed in / g were determined and are shown in Table 2 below.

[0157] [Table 2]

[0158] Example 4: Electrochemical Analysis of Impregnated Organoboron Covalent Frameworks According to the Invention Materials and Methods Sample preparation All experiments were carried out in a glove box (O2 and HO < 3 ppm) under a dry argon atmosphere. The powder was dried at 120 °C for 8 h and cold-pressed at approximately 120 MPa for 1 min to obtain pellets for electrochemical testing. The pellets are also referred to as "electrolyte" in the rest of this example. All experiments were carried out at 70 °C, except for measurements by electrochemical impedance spectroscopy.

[0159] Electrochemical Impedance Spectroscopy Electrochemical impedance spectroscopy (EIS) measurements were performed using a BioLogic MTZ-35 frequency response analyzer connected to an intermediate temperature system (ITS), with the sample temperature controlled by the Peltier effect. An electrolyte pellet with a diameter of 6 mm and a thickness of 0.7 mm was sandwiched between two blocking electrodes (30 mg; 120 MPa) for conducting ions. This metal / electrolyte / metal setup allowed us to observe only the impedance spectral behavior of the electrolyte (blocking electrode: Al).

[0160] AC impedance spectra were recorded in the frequency range from 30 MHz to 0.1 Hz with an excitation signal of amplitude 0.05 V. Measurements were performed with heating and cooling (1 °C / min) between 20 °C and 100 °C, with the temperature allowed to stabilize for 15 min before each impedance measurement.

[0161] Ionic conductivity (σ) was calculated after modeling and simulation of EIS data using an equivalent circuit model, using the following equation: σ ionic = I / (R*A), where I is the pellet thickness, R is the resistance, and A is the surface area of ​​the surface in contact with the electrode (A = πr 2, r represents the radius). The activation energy (Ea) was calculated from the slope of the Arrhenius graph. The device was attached to a sample holder (Controlled Environment Sample Holder, CESH, BioLogic) placed in a sealed cell.

[0162] Cyclic and Linear Sweep Voltammetry This type of measurement is performed using Li around 0V. + + e - = This is performed to verify the proper functioning of the electrolyte with respect to Li-ion conductivity by observing the reversibility of the Li system. This type of measurement can also verify the possibility of electrochemical degradation by evaluating parasitic currents in oxidation and reduction, which can be observed throughout the entire range of the potential being evaluated. Linear sweep voltammetry (LSV) is a simple electrochemical technique. Linear sweep voltammetry is similar to cyclic voltammetry, but instead of performing linear cycles in both directions through the potential range, a single linear sweep is performed from the lower potential limit to the upper potential limit.

[0163] This time, the thickness of the electrolyte was set to 100 μm, which is thinner than the previous one, to avoid distortion of the voltammogram due to the ohmic drop effect. 0 An asymmetric cell assembly of the / electrolyte / stainless steel (+) type is used to investigate the reversible deposition of lithium metal on the stainless steel that serves as the positive electrode of the potentiostat.

[0164] Typically, 0.1 mVs over the potential range of -0.5 to 5.0 V (vs. Li / Li+) -1 A scan rate of 100 s is applied to obtain different chronoamperograms.

[0165] Li by galvanostatic cycling + Investigation of the reversibility of the / Li electrochemical system This measurement also shows the Li + + e -= This is done to verify whether the electrolyte functions properly with respect to the ionic conductivity of Li ions by observing the reversibility of the Li system.

[0166] 0.1mA / cm 2 , 0.2mA / cm 2 , and 2mA / cm 2 At a current density of 1000 kJ / s, the symmetric cell (Li 0 / electrolyte / Li 0 The voltage at the electrode was cycled multiple times between +15 mV and −15 mV. Again, the electrolyte thickness was approximately 100 μm.

[0167] result 1. Conductivity measurement 5 to 7 show the EIS spectra of impregnated organoboron covalent frameworks based on COF-5, COF-1, and COF-10 as a function of the Li / B ratio.

[0168] Table 3 below summarizes the conductivity values ​​at 20°C and 100°C of different impregnated COFs according to the invention.

[0169] [Table 3]

[0170] These results demonstrate that the impregnated organoboron covalent structures of the present invention have electrical conductivity suitable for use as electrolytes in batteries, with some values ​​comparable to other electrolyte materials known as ceramic materials.

[0171] 2. Battery test As a first step, COF-5@LiI-impregnated COFs were tested as separators. Two batteries were prepared: one with an electrolyte consisting of only anhydrous LiI, and the other with a layer of COF-5@LiI (2Li / B) in the middle of an electrolyte consisting of anhydrous LiI. Lithium metal and Li-TCNQ were used as the anode and cathode, respectively.

[0172] These two batteries were then tested by a galvanostatic method with potential limiting. It is noteworthy that the battery with only LiI as the electrolyte / separator showed no electrochemical activity (right panel of Figure 8). In contrast, the battery containing the subject invention showed the electrochemical properties of the cathode material at 2.4 / 3 V vs. Li (left panel of Figure 8).

[0173] In the second step, a battery containing COF-5@LiI as an additive (Li-TCNQ and Li metal as the cathode and anode, respectively) was prepared by incorporating COF-5@LiI into a PEO-type polymer matrix.

[0174] The cell was tested by galvanostatic cycling with potential limiting, and the resulting curves are shown in Figure 9.

[0175] These results indicate that the presence of COF-5@LiI in the electrolyte promotes the migration of lithium ions and develops the electrochemical properties of the positive electrode material.

[0176] As a third step, a battery containing COF-5@LiI as a solid electrolyte (compressed pellets) (perylene-diimide and Li metal as the positive and negative electrodes, respectively) was prepared.

[0177] The cell was tested by galvanostatic cycling with potential limiting, and the resulting curves are shown in Figure 10.

[0178] These results indicate that COF-5@LiI can be used directly as an electrolyte to develop the electrochemical properties of cathode materials and enable the design of solid-state organic Li-metal batteries.

[0179] Example 5: LiI-impregnated COF-5 organoboron covalent framework with smaller specific surface area

[0180] 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 -3 The precursors (2000 mol) were ground together in a zirconium crucible and then dried overnight (80°C under vacuum). 3 mL of synthesis grade methanol was added to the precursor, followed by a 1:4 volume ratio mixture of mesitylene and 1,4-dioxane (i.e., 77:307 mL). The flask was placed in an ultrasonic bath for 10 minutes and then heated to 90°C with very vigorous stirring (well above 500 rpm). After stirring for 7 days, the reaction mixture was filtered. The recovered solid was then washed three times with acetone.

[0181] The obtained COF-5 was 405m 2 / g specific surface area.

[0182] The FT-IR spectrum of the COF is shown in Figure 11 ("COF-5 I"). Figure 11 shows the FT-IR spectrum of the COF with a specific surface area of ​​2068 m, obtained according to the procedure described in 1.1 above. 2 The FT-IR spectrum of COF-5 at 1000 kJ / g is also shown for comparison.

[0183] LiI impregnation The COF-5 was impregnated with a solution of lithium iodide to give a concentration of 0.83 mg LiI / m on the COF. 2 To this end, 168.1 mg of lithium iodide was used for 1 g of COF.

[0184] The impregnation procedure is as described above. Again, LiI is dissolved in 7 mL of dry acetone. The COF-5 is suspended in the solution and stirred for 7 days, after which the solvent is evaporated. The compound is thoroughly dried under vacuum following the steps described above.

[0185] The Li / B ratio of the obtained impregnated COF is 0.2.

[0186] Conductivity measurements by electrochemical impedance spectroscopy Resistivity measurements, performed as described in Example 4 above, show no conductivity at 20°C and 30°C. Between 40°C and 100°C, conductivity is observed and measurable. The conductivity value obtained is 9.81·10 -9 Scm -1 (value at 40°C) to 3.95·10 -6 Scm -1 (value at 100°C).

Claims

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

2. 2. The impregnated organoboron covalent organic framework of claim 1 , wherein the salt is a lithium salt.

3. The salt has the formula MX 1 where M is an alkali metal cation and an alkaline earth metal cation, preferably Li + , Na + , K. + , Mg 2+ and Ca 2+ , advantageously Li + and X is a metal cation selected from 1 However, preferably halide ions, perchlorate anions ClO 4 - and bis(trifluoromethanesulfonyl)imide anion. The impregnated organoboron covalent organic framework according to claim 1 or 2, wherein the anion is an anion containing at least one halogen selected from the group consisting of

4. 4. The impregnated organoboron covalent organic framework of claim 1, wherein the salt is lithium iodide.

5. 5. The impregnated organoboron covalent organic framework according to claim 1, wherein the molar ratio of the alkali metal or alkaline earth metal to the boron is between 0.05 and 10, preferably between 0.1 and 5, preferably between 0.2 and 4, preferably between 0.3 and 3.

6. The following formula (I): 【Chemistry 1】 wherein A is an optionally substituted monocyclic or polycyclic organoboron moiety, Z is an optionally substituted monocyclic or polycyclic organic moiety, and the A-Z bond is a carbon-boron bond. or having the following formula (II): 【Chemistry 2】 wherein A is an optionally substituted monocyclic or polycyclic organoboron moiety, X is an optionally substituted monocyclic or polycyclic organic moiety, and the AX bond is a carbon-boron bond. or having the following formula (III): 【Transformation 3】 wherein D is an optionally substituted monocyclic or polycyclic organic moiety, R is an optionally substituted linear organic moiety, and M' + Li + , Na + , K. + , Ca 2+ , Mg 2+ , or Al 3+ The cation is selected from metal, alkali metal, or alkaline earth metal cations such as The impregnated organoboron covalent organic framework according to any one of claims 1 to 5, wherein the organoboron covalent organic framework is a spiroborate having the formula:

7. 7. The impregnated organoboron covalent organic framework of claim 6, having the formula (I):

8. The moiety A is a moiety of formula (A-1): 【Chemistry 4】 and the portion of formula (A-2): 【Transformation 5】 wherein E is a monocyclic or polycyclic, optionally substituted, preferably aromatic, hydrocarbon moiety. The impregnated organoboron covalent organic framework according to claim 6 or 7, wherein the impregnated organoboron covalent organic framework is selected from the group consisting of:

9. 9. The impregnated organoboron covalent organic framework of claim 6, wherein the moiety Z comprises one or more optionally substituted 6-membered aromatic hydrocarbon rings, and when the moiety Z comprises multiple rings, each ring is independently fused to one or more other rings and / or each ring is separated from the other rings by at least one chemical bond.

10. 10. The impregnated organoboron covalent organic framework of claim 1 , selected from COF-1 , COF-5, and COF-10, preferably COF-5.

11. The following steps: providing an organoboron covalent structure; - adding to the organoboron covalent structure a solution of a salt selected from alkali metal salts and alkaline earth metal salts in an organic solvent to obtain a mixture; agitating the mixture; and - removing the organic solvent by drying the mixture, which drying is divided into at least a first drying step and a second drying step; 11. A method for preparing the impregnated organoboron covalent organic framework of claim 1, comprising:

12. 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. 11. Use of the impregnated organoboron covalent structure of any one of claims 1 to 10 as a solid electrolyte in an all-solid-state battery.

14. 11. Use of the impregnated organoboron covalent structure of any one of claims 1 to 10 as an additive in the composition of an electrolyte.

15. 11. An electrolyte composition comprising the impregnated organoboron covalent structure of any one of claims 1 to 10.

16. 11. A solid separator for an all-solid-state battery comprising the impregnated organoboron covalent structure of any one of claims 1 to 10.

17. 11. An electrode for an all-solid-state battery comprising the impregnated organoboron covalent framework of any one of claims 1 to 10.

18. 11. An all-solid-state battery comprising the impregnated organoboron covalent framework of any one of claims 1 to 10.

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