Composition and solid electrolyte

Abstract

The invention relates in particular to a composition consisting essentially of at least one first inorganic precursor, at least one second inorganic precursor, said inorganic precursors being dispersed in at least one organic polymer, and of which the at least one first inorganic precursor is selected from the family of alkoxymetalloids of formula M-(OR1)n with n ranging from 1 to 4 and R1 selected from hydrogen, alkyl, aryl, and / or alkenyl group, and M a metalloid element, the at least one second inorganic precursor is selected from X-(OR2)m or X-(R2)m with m ranging from 1 to 2, R2 selected from hydrogen, alkyl, aryl, and / or alkenyl group and X an alkali or alkaline-earth element, and the at least one organic polymer comprises at least one side chain. Figure to be published with the abstract: 1

Description

Title of the invention: Composition and solid electrolyte Technical field

[0001] The invention relates to the field of electrochemistry and more specifically to solid electrolytes. In particular, the invention relates to a composition, preferably a composition for a solid electrolyte.

[0002] Furthermore, the invention relates to a solid electrolyte. Prior art

[0003] In the field of electrochemistry, there are different types of electrochemical cells. An electrochemical cell usually comprises a positive electrode and a negative electrode which are separated by a separator in the presence of electrolyte. Thanks to the reactions which occur at the electrodes, the electrochemical cell is capable of producing electrical energy. In order to prevent the electrodes from coming into contact with each other and creating a short circuit, they can be separated by a separator immersed in a liquid electrolyte or directly separated by a solid electrolyte.

[0004] The electrolyte also allows the transfer of ions from one electrode to the other, reflecting a certain ionic conductivity and ensuring the operation of the electrochemical cell.

[0005] A liquid electrolyte, commonly known in lithium-ion (Li-ion) systems, comprises a solution of a lithium salt dissolved in a solvent, for example from the carbonate family, such as ethylene carbonate (EC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC) or propylene carbonate (PC).

[0006] These liquid electrolytes are particularly interesting in industry, because they offer good ionic conductivity of lithium ions.

[0007] However, liquid electrolytes have a low viscosity, which increases the risk of the electrolyte leaking out of the cell. In addition, the presence of carbonate results in a high risk of flammability, resulting in a reduction in safety.

[0008] Also, alternatives to liquid electrolytes have been developed, including solid electrolytes where the liquid electrolyte is replaced by a solid compound.

[0009] For example, the solid electrolyte may be an oxide, a ceramic-type oxide, a sulfide, or a polymer. The solid electrolyte may include a salt if necessary. In Li-ion batteries these are lithium salts.

[0010] Ceramics allow lithium to pass through and can act as a separator, eliminating the need for a microporous separator film. However, their brittleness has hampered their development and application in industry.

[0011] Solid oxides have a high mechanical strength and chemical stability, however they generally require high temperature sintering which weakens the structure. In addition, their ionic conductivity currently remains low due in particular to the resistance at grain boundaries.

[0012] Finally, solid polymer electrolytes have attractive properties in industry, particularly due to their economic potential and ease of production. In addition, they have little risk of leakage and little risk of ignition. However, they also have reduced ionic conductivity, particularly at room temperature.

[0013] In order to avoid the low conductivity of solid polymer electrolytes, gel-polymer electrolytes have been developed. In this case, the liquid electrolyte (solvent and salt) is immobilized within a polymer matrix comprising one or more polymers capable of obtaining a gel.

[0014] The solvent and salt allow the electrolyte to offer a conductivity close to that of liquid electrolytes, while the polymer matrix provides a solid structure. However, they have poor mechanical properties which makes their use difficult.

[0015] Some solid and gel electrolytes can be made from sol-gel reactions catalyzed by an acid or a base.

[0016] Indeed, in a manner known per se, a so-called sol-gel reaction is a synthesis of oxides based on the formation of oxo bridges by a succession of hydrolysis and condensation reactions. The first steps allow the production of a colloidal “sol” solution and the following ones allow the production of a “gel” gel.

[0017] Two synthesis routes predominate: the inorganic route from metal salts in aqueous solution and the polymeric route from metal or metalloid alkoxides in organic solution. The hydrolysis reaction can be initiated by adding water (alkoxy route) or by changing the pH (inorganic route). The development of oxide-polymer networks takes place from precursors, generally metal alkoxides. The hydrolysis and condensation of metal alkoxides can be considered as a nucleophilic substitution of the alkoxy by the hydrolyzed species. Thus, the reactions take place according to:

[0018] (1) M-OR + H2O M-OH + ROH conversion of alkoxy functions into hydroxy which allows to generate reactive M-OH functions

[0019] (2) M-OH + HO-M MOM + H2O condensation with oxolation and water release

[0020] (3) M-OR + HO-M MOM + ROH condensation with alkoxolation and release of a alcohol.

[0021] With M a metal or metalloid such as silicon, with R an organic group of general formula CnH2n+i.

[0022] In the specific case of silicon alkoxides, water is introduced in alcoholic solution with precursors, the most common of which are TMOS or TEOS (for tetramethoxysilane and tetraethoxysilane respectively). The hydrolysis step is particularly slow, so a catalyst is always used. This catalyst can be an acid or a base.

[0023] Furthermore, the competition between hydrolysis and condensation can be controlled thanks to the pH of the reaction.

[0024] In an acidic medium, hydrolysis is faster than condensation, the gel obtained, called “polymeric gel”, comprises a polymeric silica network trapping the solvent and molecules still in solution (in particular the catalyst and the catalysis products).

[0025] In a basic medium, condensation is generally faster and leads to porous gels called “colloidal gel” whose negatively charged silica network leaves the molecules in suspension (we also find the catalyst and catalysis product).

[0026] Thus, it may become necessary to control the reaction kinetics to add chelators, again acid or base of the acetic acid type for example.

[0027] Furthermore, the gel obtained by acid or basic catalysis also comprises solvents and precursors which have not necessarily reacted.

[0028] Thus the pH and the catalysts influence the sol-gel reaction and the gel obtained.

[0029] However, the catalysts and their reaction products in the solvent and / or gel generate high reactivity that greatly reduces the electrochemical stability of the electrolytes. In addition, the products of catalysis (acid or base) can cause unwanted oxidation side reactions on some of the functional groups. This can result in the presence of toxic or corrosive species or species that increase the dissolution of the solid electrolyte and reduce its lifetime. The high reactivity of both the base or acid and the metal will also greatly limit the applicable reaction and / or processing solvent media. These reactive bases or acids and metals are also generally sensitive to moisture and air, which requires expensive and complex manufacturing processes.Similarly, current processes do not include complex and expensive purification to remove these catalysts and their reaction products that can remain trapped in the gel and reduce its mechanical and electrochemical properties. Indeed, after obtaining the gel, it is dried (different types of drying exist) which allows the evaporation of the solvents or alcohols formed, but not the catalysts and / or their reaction products that remain harmful to the operation of an electrochemical system.

[0030] Finally, there are also sol-gel reactions involving mineral and organic species in order to obtain so-called “hybrid” electrolytes. These electrolytes are obtained from mixed precursors such as organo-alkoxysilanes which include take both hydrolyzable Si-OR functions for the formation of the silica network and Si-R functions attached to the silica skeleton.

[0031] Again, two routes predominate: post-addition of ceramic particles within the polymer matrix or by in situ generation of the inorganic part using ceramic precursors such as TEOS.

[0032] Nevertheless, the hydrolysis reaction remains initiated by acidic or basic catalysts for example HCl or NaOH and therefore generates the same drawbacks as the sol-gel routes of solid or gelled electrolytes due to the residual presence of the reaction products.

[0033] Thus, there is a need for new compositions and processes capable of doing without the use of traditional catalysts (acid or basic).

[0034] The invention aims to overcome the drawbacks of the prior art. In particular, the invention aims to propose a composition not comprising a traditional acidic and / or basic catalyst and making it possible to meet the needs of the field of electrochemistry.

[0035] Thus, the invention aims to propose a solid electrolyte, said solid electrolyte not comprising any acid or basic catalyst residue and making it possible to meet the requirements of the field of electrochemistry, namely, in particular good ionic conductivity and good mechanical and electrochemical properties (i.e. electrochemical stability). In the present invention, the catalyst is a component of the final system and therefore no longer has to be eliminated. Summary of the invention

[0036] The invention aims to overcome the disadvantages of the prior art. The following presents a simplified summary of selected aspects, embodiments and examples of the present invention for the purpose of providing a basic understanding of the invention. However, this summary does not constitute an exhaustive overview of all aspects, embodiments and examples of the invention. Its sole purpose is to present selected aspects, embodiments and examples of the invention in a concise form as an introduction to the more detailed description of the aspects, embodiments and examples of the invention which follow the summary.

[0037] The invention relates in particular to a composition consisting essentially, for example consisting of, at least one first inorganic precursor, at least one second inorganic precursor, said inorganic precursors being dispersed in at least one organic polymer, and of which: - The at least one first inorganic precursor is selected from the family of alkoxymetalloids of formula M-(0Ri)n with n ranging from 1 to 4 and Ri selected from hydrogen, alkyl, aryl, and / or alkenyl group, and M a metalloid element, - The at least one second inorganic precursor is selected from X-(OR2)m or X-(R2)m with m ranging from 1 to 2, R2 selected from hydrogen, alkyl, aryl and / or alkenyl group and X an alkali or alkaline-earth element, and - The at least one organic polymer comprises at least one side chain.

[0038] Such a composition makes it possible to do without the use of traditional catalysts (acid or basic) while still meeting the needs of the field of electrochemistry.

[0039] The composition according to the invention makes it possible to avoid the need for purification or elimination of catalysts and / or reaction products.

[0040] Furthermore, the composition according to the invention allows the combination and preferably the dispersion of inorganic precursors within at least one organic polymer. The composition allows intimate mixing of inorganic precursors with at least one organic polymer. The composition allows different applications and in particular applications in electrochemistry. In addition, such a composition allows stabilization of the components and in particular the ionic components within the at least one organic polymer.

[0041] According to other optional characteristics of the composition, the latter may optionally include one or more of the following characteristics, alone or in combination: - the at least one organic polymer is a star polymer; - the at least one organic polymer is selected from polyoxide or co- polyalkylene oxide(s), polymethacrylate, polyacrylate, polysaccharide, polyacrylonitrile, polyimide and / or (co)polymers of VF2 (for vinyldiene fluoride), their derivative and / or their mixture. - the alkali or alkaline-earth element is selected from: Li, Na, K, Be and / or Mg; - the metalloid element is selected from Si and / or B; - it further comprises at least one salt, preferably one or more lithium salts; - it also includes inorganic particles.

[0042] According to a second object, the invention relates to a use of the composition according to the invention for forming a solid electrolyte. Such use makes it possible to facilitate the formation of a solid electrolyte (absence of purification and / or elimination of catalyst, reaction product).

[0043] According to a third object, the invention relates to a solid electrolyte, characterized in that it comprises at least one inorganic network, having at least one element alkaline or alkaline-earth, dispersed in at least one organic polymer, said inorganic network corresponding to a condensation between at least one first inorganic precursor and at least one second inorganic precursor, The at least one first inorganic precursor is selected from the family of alkoxymetalloids of formula M-(ORi)n with n ranging from 1 to 4 and Ri selected from hydrogen, alkyl, aryl, and / or alkenyl group, and M a metalloid element, The at least one second inorganic precursor is selected from X-(OR2)m or X-(R2)m with m ranging from 1 to 2, R2 selected from hydrogen, alkyl, aryl and / or alkenyl group and X an alkali or alkaline-earth element, and The at least one organic polymer comprises at least one side chain.

[0044] A solid electrolyte according to the invention makes it possible to exhibit good mechanical and electrical properties and in particular ionic conductivity as well as an improved electrochemical stability voltage window. Indeed, the electrolyte according to the invention is not liquid while being manipulable and stretchable without breaking or collapsing. Advantageously, the solid electrolyte exhibits good homogeneity of the structure of the electrolyte, preferably at the submicron scale, and good purity (absence of catalyst and residues).

[0045] In addition, the solid electrolyte according to the invention also has good stability due to the absence of reaction products of acidic or basic catalysts. In addition, the solid electrolyte according to the invention does not include any toxic, corrosive or dissolution-increasing species. The presence of an inorganic fraction improves the electrochemical stability voltage window.

[0046] According to other optional characteristics of the electrolyte according to the invention, the latter may optionally include one or more of the following characteristics, alone or in combination: the at least one organic polymer comprises a condensation of the at least one first inorganic precursor with the at least one second inorganic precursor in its hydrolyzed form to form an inorganic network, said inorganic network condensing with the at least one organic polymer to form an organic / inorganic hybrid network.

[0047] According to a fourth object, the invention relates to a use of a solid electrolyte according to the invention in electrochemical devices of the accumulator, battery, capacitor, electrochemical double-layer electric capacitor, membrane-electrode assembly (MEA) for fuel cell or electrochromic device types.

[0048] According to a fifth object, the invention relates to a film obtained from the composition according to the invention. Description of the embodiments

[0049] Other characteristics and advantages of the invention will be better understood on reading the description which follows and with reference to the appended drawings, given for illustrative purposes and in no way limiting.

[0050] [Fig.lA] [Fig.lA] represents a graph of analysis of the chemical environment by XPS (for X-Ray Photo-electron Spectroscopy in English terminology) of the Si 2p of a solid electrolyte according to an embodiment of the invention.

[0051] [Fig.IB] [Fig.IB] represents a graph of analysis of the chemical environment by XPS of the O 1 s of a solid electrolyte according to an embodiment of the invention

[0052] [Fig.lC] [Fig.lC] represents a graph of analysis of the chemical environment by XPS of the Si 2p of a solid electrolyte according to an embodiment of the invention after calcination.

[0053] [Fig.lD] [Fig.lD] represents a graph of analysis of the chemical environment by XPS of the O 1 s of a solid electrolyte according to an embodiment of the invention after calcination.

[0054] [Fig.2] [Fig.2] represents a thermogram of a solid electrolyte with different silica levels.

[0055] [Fig.3A] [Fig.3A] represents a graph of the conductivity as a function of the temperature of a solid electrolyte according to different silica levels.

[0056] [Fig.3B] [Fig.3B] represents a graph of conductivity versus temperature of a solid electrolyte as a function of different LiTFSI levels.

[0057] [Fig.3C] [Fig.3C] represents a graph of the intensity as a function of the potential of a virgin polymer (PEO) and a solid electrolyte (CPE for composite polymer electrolyte in English terminology) according to an embodiment of the invention in the presence of lithium salt PEO:Li of 20:1 and at 25°C.

[0058] Below, we describe a summary of the invention and the associated vocabulary, before presenting the disadvantages of the prior art, and then finally showing in more detail how the invention overcomes them.

[0059] In the remainder of the description, the term "solvent" means a substance, liquid or supercritical at its temperature of use, which has the property of solubilizing, diluting or extracting other substances without modifying them chemically and without itself modifying itself.

[0060] By "polymer" is meant either a copolymer or a homopolymer. By "copolymer" is meant a polymer grouping together several different monomer units and by "homopolymer" is meant a polymer grouping together identical monomer units. By "block copolymer" is meant a polymer comprising one or more uninterrupted sequences of each of the distinct polymer species, the polymer sequences being chemically different from each other and being linked together by a covalent bond. These polymer sequences are also called polymer blocks.

[0061] The term “polymerization” within the meaning of the invention designates the process of converting a monomer or a mixture of monomers into a polymer.

[0062] The term “monomer”, within the meaning of the invention, designates a molecule which can undergo polymerization.

[0063] The term “solid electrolyte” within the meaning of the invention may designate an electrolyte which does not flow under the effect of its own weight, preferably over a duration acceptable in the field (for example over an order of magnitude of an hour).

[0064] The expression, "consists essentially" within the meaning of the invention may mean that the composition is composed of the constituents cited in the present application, preferably is composed only of the constituents cited in the present application, namely at least one first precursor, at least one second precursor, and at least one organic polymer; optionally supplemented by one or more salts, solvents and / or inorganic particles. It may optionally comprise other components provided that the latter do not substantially modify the nature and properties of the composition.

[0065] The invention is now described in more detail and in a non-limiting manner in the following description. In the remainder of the description, the same references are used to designate the same elements.

[0066] The invention proposes to take into consideration the drawbacks of the prior art while taking into account the needs in the field of electrochemistry.

[0067] The composition within the meaning of the invention essentially consists, for example it consists of, at least one first inorganic precursor, at least one second inorganic precursor and at least one organic polymer, the at least first inorganic precursor and the at least one second inorganic precursor being dispersed in the at least one organic polymer.

[0068] ORGANIC POLYMER

[0069] The at least one organic polymer within the meaning of the invention may correspond to a polymer comprising at least one side chain, preferably at least two, more preferably at least three and even more preferably at least four. In a preferred, but non-limiting, embodiment of the invention, the at least one organic polymer may be a so-called "star" or branched or comb-like polymer.

[0070] The at least one organic polymer within the meaning of the invention may correspond to a copolymer and / or a homopolymer.

[0071] The at least one organic polymer within the meaning of the invention may be a thermoplastic polymer. A thermoplastic polymer means a polymer which is generally solid at room temperature, which may be crystalline, semi-crystalline or amorphous, and which softens upon increasing temperature, in particular after having exceeded its glass transition temperature (Tg) and having flowed at a higher temperature and having been able to observe a clear melt upon exceeding its temperature called melting temperature (Tf) (when it is semi-crystalline), and which becomes solid again when the temperature drops below its melting point and below its glass transition temperature.

[0072] The at least one organic polymer within the meaning of the invention is preferably solid at room temperature, this avoids the risks of collapse or leakage and promotes the maintenance of the polymer network.

[0073] Advantageously, the at least one organic polymer within the meaning of the invention may be functionalized. For example, a functionalized organic polymer may comprise at least one chemical group of hydroxy, amine, halogen, alcohol, epoxy, acid and / or anhydride type to influence (i.e. improve) the electrical and / or mechanical and / or chemical properties (polymer network, formation of chemical bond, ionic conductivity) of the at least one organic polymer, preferably with the at least one first inorganic precursor and / or the at least one second inorganic precursor.

[0074] In a preferred but non-limiting embodiment of the invention, the at least one functionalized organic polymer may comprise at least one hydroxy function.

[0075] Preferably, the at least one organic polymer has a weight-average molecular mass ranging from 1000 g / mol to 500000 g / mol, preferably ranging from 10000 g / mol to 300000 g / mol, and even more preferably ranging from 15000 g / mol to 250000 g / mol. The weight-average molecular mass can be measured by size exclusion chromatography (SEC).

[0076] The at least one organic polymer within the meaning of the invention may be selected from polyoxide or copolyoxide of alkylene(s), polymethacrylate, polyacrylate, polysaccharide, polyacrylonitrile, polyimide and / or (co)polymers of VF2 (for vinylidene fluoride), their derivative and / or their mixture.

[0077] Preferably, the at least one organic polymer within the meaning of the invention may be chosen from homopolymers and / or copolymers of ethylene oxide (eg POE, copolymer of POE), propylene oxide, epichlorohydrin, allylglycidyl ether; halogenated polymers such as homopolymers and / or copolymers of vinyl chloride, vinylidene fluoride (PVDF for polyvinylidene fluoride in English terminology), vinylidene chloride, ethylene tetrafluoride, or chlorotrifluoroethylene, copolymers of vinylidene fluoride and of hexafluoropropylene (PVDF-co-HFP); homopolymers and / or copolymers of (meth)acrylate such as poly(methylmethacrylate); homopolymers and / or copolymers of polyacrylonitrile (PAN) and / or their mixtures.

[0078] Furthermore, the at least one organic polymer is present in a mass quantity ranging from 30 to 95% in the composition, preferably in an amount ranging from 33 to 90% and even more preferably in an amount ranging from 38 to 85%.

[0079] FIRST INORGANIC PRECURSOR

[0080] The at least one first inorganic precursor is selected from the family of alkoxymetalloids of formula M-(0Ri)n, with n ranging from 1 to 4, Ri selected from hydrogen, alkyl, aryl and / or alkenyl group and M a metalloid element.

[0081] Each Ri group may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, substituted aralkyl, alkenyl, and / or substituted alkenyl.

[0082] An alkyl group may comprise one or more derivatives of alkanes and / or their substituents, linear and / or branched and / or cyclic, for example methyl, ethyl, propyl, butyl, phenyl, tolyl, xylyl, mesityl, naphthyl and / or their mixture.

[0083] An aryl group may comprise a functional group which is derived from an alkyl group having lost a hydrogen for example and / or their derivatives (i.e. substituted and group) and / or their mixture.

[0084] An alkenyl group may comprise one or more derivatives of an aryl group having lost a hydrogen, for example and / or their derivatives and / or their mixture, for example vinyl, ethenyl and / or ethene.

[0085] A metalloid element is defined by the classification and can correspond to an atom of Boron (B), Silicon (Si), Germanium (Ge), Arsenic (As), Antimony (Sb), Tellurium (Te) and / or Polonium (Po).

[0086] Preferably, a metalloid element is selected from silicon and / or boron and more preferably silicon.

[0087] Preferably, the at least one first inorganic precursor comprises a silyl ether, preferably silicon tetraoxyalkyl.

[0088] Another particular example may include the methylsilane group (TMS, DMS, DMPS, MDPS, DMIPS and their derivatives), the ethylsilane group (TES and its derivatives), the isopropylsilane group (TIPS and its derivatives), the TBS group (tert-butyldimethylsilane and its derivatives), the tert-butyldiphenylsilane group and its derivatives (TBDPS), the phenylsilane group and its derivatives, the trialkylsilane group and its derivatives, the propylsilane group and its derivatives and / or the hexylsilane group and its derivatives.

[0089] For example, the at least one first inorganic precursor may be selected parmi methyltrimethoxysilane (CH3Si(OCH3)3), methyltriethoxysilane (CH3Si(OC2H5)3 ), ethyltrimethoxysilane (C2H5Si(OCH3)3), ethyltriethoxysilane (C2H5Si(OC2H5)3), pro-pyltrimethoxysilane (C3H7Si(OCH3)3), propyltriethoxysilane (C3H8Si(OC2H5)3), isobu-tyltrimethoxysilane (i-C4H9Si(OCH3)3), pentyltriethoxysilane (C6H5Si(OC2H5)3), octyl-triethoxysilane (C8Hi7Si(OC2H5)3), octadecyltrimethoxysilane (Ci8H37Si(OCH3)3), octa-decyltriethoxysilane (Ci8H37Si(OC2H5)3), phenyltrimethoxysilane (C6H5Si(OCH3)3), te-tramethoxysilane (Si(OCH3)4), tétraéthoxysilane (Si(OC2H5)4), tetrapropoxysilane (Si(O-n-C3H7)4), tetraisopropoxysilane (Si(O-i-C3H7)4), tetrabutoxysilane Si(O-n-C4H9) 4), tetrakis(s-butoxy)silane (Si(O-sec-C4H9)4), tetrakis(2-ethyl-butoxy)silane (Si(OCH2 CH(C2H5)2)4), tetrakis(2-ethyl-hexoxy)silane (Si(OCH2CH(C2H5)(C4H9))4), etrakis(2-methoxy-ethoxy)silane (Si(OCH2CH2OCH3)4) , tetraphenoxysilane (Si(OC6H5 )4, tetracetoxysilane (Si(OOCCH3)4), methyltriacetoxysilane (CH3Si(OOCCH3)3,ethyl-triacetoxysilane (C2H5Si(OOCCH3)3), di-t-butoxydiacetoxysilane ((t-C4H9 O)Si(OOCCH3)2), triethoxysilane( C6Hi6O3Si), dimethylethoxysilane (C4Hi2OSi), me-thyldiethoxysilane (C6Hi6O2Si), diphenyldiethoxysilane (Ci6H20O2Si), n-octyltriethoxysilane (Ci4H32O3Si), phenyltrimethoxysilane (C9H[4O3Si), their mixtures, and / or their derivatives (i.e. substituted and group).

[0090] For example, the at least one first inorganic precursor may be selected from: Tetramethoxysilane (TMOS), Tetraethoxysilane (TEOS), Propyltriethoxysilane (C9H22O3Si), diphenyldiethoxysilane (Ci6H20O2Si) ethyltriethoxysilane (C8H20O3Si), methyltriethoxysilane (C7Hi8O3Si), n-octyltriethoxysilane (Ci4H32O3Si), phenyltriethoxysilane (Ci2H20O3Si), and / or phenyl trimethoxysilane (C9Hi4O3Si).

[0091] Furthermore, the at least one first inorganic precursor may be present in a mass quantity ranging from 0.5 to 30% in the composition, preferably in an amount ranging from 1 to 20% and even more preferably in an amount ranging from 1 to 15%.

[0092] At least one first inorganic precursor allows the creation of chemical bonds with the at least one organic polymer and / or with the at least one second inorganic precursor.

[0093] This also makes it possible to contribute to the dispersion of the first inorganic precursor in the at least one organic polymer.

[0094] Advantageously, the at least one first inorganic precursor makes it possible to provide a metalloid and particularly preferably Si, particularly preferred in electrochemistry.

[0095] Furthermore, the at least one first inorganic precursor makes it possible to provide activatable and / or reactive chemical functions in the composition.

[0096] In addition, the presence of inorganic precursor makes it possible to participate in and improve the mechanical properties.

[0097] SECOND INORGANIC PRECURSOR

[0098] The at least one second inorganic precursor is selected from X-(OR2)m or X-(R2)m with m ranging from 1 to 2, R2 selected from hydrogen, alkyl, aryl and / or alkenyl group and X an alkali or alkaline-earth element.

[0099] An alkali element is defined by the classification and may correspond to an atom of lithium (Li), sodium (Na), potassium (K), rubidium (Ru), and / or cesium (Ce).

[0100] Preferably, an alkali element is selected from Li, Na and / or K, and more preferably Li.

[0101] An alkaline earth element is defined by classification and may correspond to a beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and / or barium (Ba) atom.

[0102] Preferably, an alkaline earth element is selected from Be and / or Mg.

[0103] Thus, an alkali or alkaline-earth element can be selected from: Li, Na, K, Be and / or Mg.

[0104] Each R2 group may independently be alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted aryl, substituted aralkyl, alkenyl, and / or substituted alkenyl.

[0105] An alkyl group may comprise one or more derivatives of alkanes and / or their substituents, linear and / or branched and / or cyclic, for example methyl, ethyl, propyl, butyl, tert-butyl, phenyl, tolyl, xylyl, mesityl, naphthyl, etc. and / or their mixture.

[0106] An aryl group may comprise a functional group which is derived from an alkyl group having lost a hydrogen for example and / or their derivatives (i.e. substituted) and / or their mixture.

[0107] An alkenyl group may comprise one or more derivatives of an aryl group having lost a hydrogen, for example and / or their derivatives and / or their mixture, for example vinyl, ethenyl, ethene.

[0108] Preferably, the at least one second inorganic precursor comprises a lithium alcoholate and / or a lithium alkoxy alcoholate.

[0109] For example, the at least one second inorganic precursor may be selected from lithium isopropoxide, lithium ethoxide, lithium tert-butoxide, and / or lithium 2-methoxy ethoxide.

[0110] Furthermore, the at least one second inorganic precursor may be present in a mass quantity ranging from 0.5 to 30% in the composition, preferably in a mass quantity ranging from 1 to 20%, preferably in a mass quantity ranging from 1 to 15% and more preferably ranging from 1 to 10%.

[0111] Furthermore, the molar ratio between the at least one first inorganic precursor and the at least one second inorganic precursor may be between 0.1 and 10 in the composition, preferably between 0.5 and 5 and more preferably between 0.9 and 2.

[0112] Advantageously, the at least one second inorganic precursor allows the insertion of an alkali or alkaline-earth element into the inorganic network (dispersed in the at least one organic polymer and the at least one first inorganic precursor). Thus, the composition and in particular the inorganic phase is enriched in alkali or alkaline-earth element. In a preferred, but non-limiting, embodiment, the at least one second inorganic precursor allows the addition of lithium ion into the composition.

[0113] The at least one second inorganic precursor also promotes ionic concentration. The at least one second inorganic precursor is the catalyst for the reaction.

[0114] OTHERS

[0115] The composition according to the invention may also comprise, preferably consist of, other components.

[0116] In one embodiment, the composition may further comprise at least one salt. A salt may correspond within the meaning of the classification to a metal such as an alkali, alkaline earth, transition and / or other metal. Preferably, the composition may further comprise one or more lithium, sodium, and / or potassium salts. More preferably, at least one salt may comprise at least one alkali metal and more preferably a lithium. One or more lithium salts may be chosen from: Lithium bis-(oxalato)borate (LiBOB or LiB(C2O4)2)); Lithium hexafluorophosphate (LiPF6); lithium fluorate (LiFO3); lithium metaborate (LiBO2); Lithium perchlorate (LiClO4); lithium nitrate (LiNO3); Lithium hexafluoroarsenate (LiAsF6); Lithium tetrafluoroborate (LiBF4); Lithium 4,5-dicyano-2-(trifluoromethyl)imidazol-l-ide (LiTDI); Lithium bis(fluorosulfonyl)imide (LiFSI);lithium trifluoromethanesulfonate (LiTF), lithium bis-trifluoromethanesulfonimide (LiTFSI); lithium N-fluorosulfonyltrifluoro-methansulfonylamide (Li-FTFSI); lithium tris(fluorosulfonyl)methide (Li-FSM); lithium bis(perfluoroethylsulfonyl)imide (LiBETI); lithium difluoro(oxalate)borate (LiDFOB); lithium 3-polysulfide sulfolane (LiDMDO), lithium trifluoroacetate (CF3COOLi), dilithium dodecafluorododecaborate (Li2Bi2Fi2), lithium bis(oxalate)borate (LiBC4O8), lithium mineral polysulfides (SyLi with y greater than or equal to 2), their derivatives and / or their mixtures. ;

[0117] The composition may further comprise at least one salt in a mass quantity ranging from 1 to 49% of the total weight of the composition, preferably in an amount ranging from 1 to 20% and even more preferably in an amount ranging from 5 to 20%.

[0118] Advantageously, the at least one organic polymer makes it possible to promote the dissociation of the salt and the transport of the ions.

[0119] The composition may also further comprise inorganic particles.

[0120] The inorganic particles preferably have a particle size of less than 50 μm. This particle size can be measured using known techniques, for example by laser particle size measurement.

[0121] Inorganic particles within the meaning of the invention may comprise ceramics, preferably conductive ceramics.

[0122] Thus in embodiments, the composition may consist essentially, preferably consist of at least one first inorganic precursor, at least one second inorganic precursor and at least one organic polymer and / or at least one ionic salt, and / or at least inorganic particles and / or at least one solvent.

[0123] In a particular embodiment of the invention, the composition may consist essentially, preferably consist of at least one first inorganic precursor, at least one second inorganic precursor, at least one organic polymer, and at least inorganic particles.

[0124] In a particular embodiment of the invention, the composition may consist essentially, preferably consist of at least one first inorganic precursor, at least one second inorganic precursor, at least one organic polymer, and at least one salt.

[0125] In a particular embodiment of the invention, the composition may consist essentially, preferably consist of at least one first inorganic precursor, at least one second inorganic precursor, at least one organic polymer, at least one ionic salt and inorganic particles.

[0126] In a particular embodiment of the invention, the composition may consist essentially, preferably consist of at least one first inorganic precursor, at least one second inorganic precursor, at least one organic polymer, and at least one solvent.

[0127] In a particular embodiment of the invention, the composition may consist essentially, preferably consist of at least one first inorganic precursor, at least one second inorganic precursor, at least one organic polymer, at least one solvent and at least one ionic salt.

[0128] In a particular embodiment of the invention, the composition may consist essentially, preferably consist of at least one first inorganic precursor, at least one second inorganic precursor, at least one organic polymer, at least one solvent and at least inorganic particles.

[0129] In a particular embodiment of the invention, the composition may consist essentially, preferably consist of at least one first precursor in organic, at least one second inorganic precursor, at least one organic polymer, at least one solvent, at least one ionic salt, and at least inorganic particles.

[0130] The composition does not comprise an additional acid and / or base catalyst and / or acid and / or base chelator, since the second inorganic precursor acts as such.

[0131] Such a composition according to the invention allows the combination and preferably the dispersion of inorganic precursors within at least one organic polymer. The composition allows intimate mixing of inorganic precursors with at least one organic polymer. The composition allows different applications and in particular applications in electrochemistry. In addition, such a composition allows stabilizing the components and in particular the ionic components within the at least one organic polymer.

[0132] USE

[0133] The composition may be used for a solid electrolyte, preferably for forming a solid electrolyte. The composition may be for forming a solid electrolyte, preferably for forming a solid electrolyte.

[0134] Thus the invention relates to the use of the composition for forming preferably specifically a solid electrolyte. The use of the composition for solid electrolyte allows control of chemical reactions and in particular of the initiation of sol-gel reactions. In addition, thanks to the use of such a composition without catalyst, there is no reaction residue present and the solid electrolyte will have better electrochemical stability.

[0135] Furthermore, the composition may be used in the form of a film, preferably to form a film, preferably to specifically form a film according to techniques known to those skilled in the art. Thus, the invention also relates to a film obtained from the electrochemical composition and preferably a solid polymer film. For example, the composition may be deposited on a support so that after polymerization it forms said film.

[0136] SOLID ELECTROLYTE

[0137] According to another aspect, the invention relates to a solid electrolyte. A solid electrolyte is capable of being obtained from the composition according to the invention. Preferably, the invention relates to a solid electrolyte obtained from the composition according to the invention.

[0138] A solid electrolyte may correspond to a separator, a component of a separator, a component of a catholyte, a component of an anolyte, a component of an accumulator, a battery, a capacitor, an electrochemical double-layer electric capacitor, a membrane-electrode assembly (MEA) for a fuel cell combustible or an electrochromic device.

[0139] Thus the invention also relates to the use of a solid electrolyte according to the invention, in electrochemical devices of the accumulator, battery, capacitor, electrochemical double-layer electric capacitor, membrane-electrode assembly (MEA) type for fuel cell or electrochromic device.

[0140] A solid electrolyte may comprise an inorganic polymer mixed in at least one organic polymer.

[0141] ORGANIC POLYMER

[0142] An organic polymer may correspond to a polymer within the meaning of the invention as disclosed above.

[0143] INORGANIC POLYMER

[0144] An inorganic polymer may correspond to the condensation of at least one first inorganic precursor, preferably according to the invention, with at least one second inorganic precursor, preferably according to the invention.

[0145] Indeed, as a result of hydrolysis and polycondensation reactions of inorganic alkoxides, a three-dimensional oxide network is formed.

[0146] One of the main advantages of such an inorganic polymer is its perfect compatibility with a wide variety of alkoxide precursors, as well as the solubility of its precursors in common organic solvents (alcohol, THF, etc.)

[0147] The presence of at least one second inorganic precursor allows the addition of metal ions within the siloxanes formed. The hydrolyzed products will condense and result in gelation.

[0148] Such an inorganic polymer allows sol-gel reactions and the formation of oxo bridges which are particularly advantageous in electrochemistry while comprising additional ions.

[0149] Furthermore, in a particular, but non-limiting, embodiment, the at least one organic polymer comprises a condensation of the at least one first inorganic precursor with the at least one second inorganic precursor in its hydrolyzed form to form an inorganic network. Said inorganic network (i.e. inorganic polymer) condenses with water minus an organic polymer to form an organic / inorganic hybrid network. Furthermore, the mass ratio between the inorganic polymer and the organic polymer may correspond to a value ranging from 0.01 to 0.5, preferably ranging from 0.05 to 0.25.

[0150] The presence of an inorganic polymer makes it possible to replace the addition of acid and / or base necessary to initiate the sol-gel reactions with precursors, preferably lithiated precursors included in the composition of the inorganic phase. In addition, lithium ions can improve the electrical properties, in particular the ionic conduction properties of the solid electrolyte.

[0151] Indeed, the use of an alcoholate, preferably a lithium alcoholate, makes it possible to initiate the sol-gel reaction in combination with an alkoxide precursor, preferably a silicon alkoxide, leading to the formation of an inorganic network enriched in lithium.

[0152] The solid electrolyte is therefore advantageously enriched with an alkaline or alkaline-earth element and preferably with lithium.

[0153] Furthermore, this new route from an inorganic precursor allows a condensation of two metal alkoxides (an alkali or alkaline-earth element reactive with an alkoxymetalloid to generate an in situ sol-gel reaction in a polymer matrix).

[0154] The synthesis of the solid electrolyte in the presence of at least one organic polymer by hydrolysis of alkoxymetalloid precursor in the presence of precursor comprising an alkali or alkaline-earth element which acts as catalyst and co-precursor leads to a fully amorphous composite with a hybrid silica network and enriched in alkali or alkaline-earth element. The solid electrolyte preferably consists of silica and lithium metasilicate (Li-Si bound) in the inorganic phase and has ionic conductivity in the absence of lithium salt, showing that the Li+ of the inorganic fraction is also involved in the Li+ transport process. Example below.

[0155] In addition, the presence of an inorganic fraction improves the electrochemical stability voltage window.

[0156] The solid electrolyte may comprise, in the presence of lithium salts, an ionic conductivity of at least 105 S / cm at 25°C, obtained by electrochemical impedance spectroscopy. Preferably, the solid electrolyte may comprise, in the presence of lithium salts, an ionic conductivity of at least 10 4 S / cm at 25°C, more preferably of at least 0.5.10 4 S / cm at 25°C.

[0157] Advantageously, the solid electrolyte has good homogeneity of the structure of the electrolyte, preferably on a submicron scale, and good purity (absence of catalyst and residues).

[0158] The solid electrolyte also has good mechanical properties and ionic conductivity. The gel obtained during the sol-gel reaction has good condensation, close to 100%. Indeed, it is not liquid while being manipulable and stretchable without breaking or collapsing.

[0159] A solid electrolyte according to the invention has an improved lifetime. A solid electrolyte also has good mechanical and electrical properties. In addition, the solid electrolyte according to the invention also has good stability due to the absence of reaction products of acidic or basic catalysts. In addition, the solid electrolyte according to the invention does not comprise any toxic, corrosive or which increases its dissolution.

[0160] According to another aspect, the invention relates to a method for manufacturing a solid electrolyte comprising an organic and inorganic hybrid network. Preferably, it is a method for manufacturing a solid electrolyte according to the invention.

[0161] A manufacturing method according to the invention may comprise a step of preparing a composition, preferably in solution in a solvent, comprising at least one organic polymer comprising at least one side chain and at least one first inorganic precursor selected from the family of alkoxymetalloids of formula M-(ORl)n with n ranging from 1 to 4 and RI selected from hydrogen, alkyl, aryl, and / or alkenyl group, and M a metalloid element.

[0162] A solvent may correspond to a usual solvent for sol-gel reactions.

[0163] For example, a solvent may correspond to THF, acetone, DMF.

[0164] The step of preparing a composition may comprise adding at least one salt and preferably at least one lithium salt to the composition and more preferably as disclosed above.

[0165] The step of preparing a composition may comprise adding inorganic particles, preferably inorganic particles as also disclosed above.

[0166] During the step of preparing the composition, the mass ratio between the at least one first inorganic precursor and the at least one organic polymer may be greater than or equal to 0.01, preferably greater than or equal to 0.03.

[0167] During the step of preparing the composition, the mass ratio between the at least one first inorganic precursor and the at least one organic polymer may be less than or equal to 0.50, preferably less than or equal to 0.25.

[0168] The step of preparing a composition does not comprise an acid and / or basic catalyst.

[0169] The preparation step can be carried out using equipment (i.e. scales, mixer, etc.) and glassware usually used in the field.

[0170] The method for manufacturing a solid electrolyte may comprise a step of adding at least one second inorganic precursor selected from X-(OR2)m or X-(R2)m with m ranging from 1 to 2, R2 selected from hydrogen, alkyl, aryl and / or alkenyl group and X an alkali or alkaline-earth element. Preferably at least one second inorganic precursor as disclosed above.

[0171] The addition step can be carried out using a pipette and other equipment allowing addition preferably drop by drop.

[0172] During the step of adding the at least one second inorganic precursor, the mass ratio between the at least one second inorganic precursor and the at least one organic polymer may be greater than or equal to 0.010, preferably greater than or equal to equal to 0.015.

[0173] During the step of adding the at least one second inorganic precursor, the mass ratio between the at least one second inorganic precursor and the at least one organic polymer may be less than or equal to 0.50, preferably less than or equal to 0.1.

[0174] During the step of adding the at least one second inorganic precursor, the molar ratio between the at least one first inorganic precursor and the at least one second inorganic precursor may be greater than or equal to 0.1.

[0175] During the step of adding the at least one second inorganic precursor, the molar ratio between the at least one first inorganic precursor and the at least one second inorganic precursor may be less than or equal to 10, preferably less than or equal to 5 and more preferably less than or equal to 2.

[0176] The manufacturing process may comprise a step of forming a preparation by hydrolysis and condensation of the composition so as to form an inorganic network loaded with an alkali or alkaline-earth element. The hydrolysis step may be initiated using the precursors. Indeed, the addition of two inorganic precursors according to the invention makes it possible to initiate the sol-gel reaction. In particular, the second inorganic precursor acts as a strong base once hydrolyzed to initiate this reaction. The reaction products (water / alcohol) can be easily removed. For example, the process may comprise a drying and / or evaporation step to remove said products. Drying may, for example, correspond to vacuum drying. The reaction leads to the formation of an inorganic network within the polymer matrix. Thus, the process according to the invention does not comprise catalysis.Furthermore, during the formation of the inorganic network within the matrix, some of the alkali or alkaline-earth elements remain trapped in the inorganic network within the polymer matrix, which makes it possible to enrich the inorganic network within the polymer matrix with alkali or alkaline-earth elements.

[0177] The method may comprise a step of forming a solid electrolyte from the preparation. The forming step may comprise dip-coating, spin-coating, roll coating, doctor blade, electrospraying, or electrophoresis.

[0178] The manufacturing process according to the invention makes it possible to dispense with the step of adding an acid and / or basic catalyst and / or an acid and / or basic chelator other than the second inorganic precursor. Thus, the process according to the invention makes it possible to facilitate the manufacture of a solid electrolyte.

[0179] Furthermore, the method according to the invention makes it possible to broaden the choice of media, solvents.

[0180] A particular example of the invention is illustrated below. This example illustrates a preferred route, but does not limit the invention to this particular example.

[0181] EXPERIENCE

[0182] Material

[0183] The experiments were carried out with a 4-pointed star-shaped poly(ethylene oxide)-sta-poly(propylene oxide) (PEOno-staLPPOso) with a molar mass of 9500 g / mol. Also used were anhydrous tetrahydrofuran (THF, >99.9%, without inhibitor), tetraethyl orthosilicate (TEOS, 98%), lithium tert-butoxide solution (LitBuO, IM in THF, 95%) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, 99%).

[0184] Synthesis

[0185] Star-type PEO-stat-PPO (hereinafter PEO) was mixed with LiTFSI and solubilized with THF at various ethoxide / lithium molar ratios (20:1, 13:1, 10:1, 8:1) in a 20 ml vial at 30% grams per 100 ml. The appropriate amount of TEOS was added dropwise to the mixture using a micropipette. The mixture was stirred with a magnetic stirrer for 15 minutes before the rapid addition of a lithium tert-butoxide solution with an equivalent molar ratio to TEOS. The final preparation was stirred overnight before being cast onto stainless steel and dried under vacuum at 80 °C for 24 hours.

[0186] The solid electrolytes were prepared via a non-hydrolytic sol-gel reaction using both silica and lithium-based precursors. Lithium tert-butoxide (LitBuO) was used as the lithium-based precursor and also acted as a catalyst (reaction initiator). Indeed, with a pKa of about 19.2, lithium tert-butoxide acts as a base to activate the hydrolysis and condensation of the inorganic precursors. All reactants were miscible in THF, leading to a homogeneous composition before the sol-gel reactions.

[0187] The synthesis of the preparation was carried out in three steps: solubilization of the polymer and the lithium salt in THF, followed by the addition of TEOS, and then lithium tert-butoxide which was added to initiate hydrolysis and condensation. Such reactions can be visually observed during the process due to the increase in viscosity of the mixture. After drying, the preparation was cast onto a stainless steel plate. No additional acid or alkaline catalyst to activate the sol-gel reaction was used. This is an advantage in terms of the purity of the solid electrolyte, as only ethanol and water are formed and eliminated during drying.

[0188] To characterize the chemical interactions and the nature of the inorganic network, an XPS analysis was performed on both the solid electrolyte sample as synthesized and on the calcined sample (i.e., removal of the organic phase without modifying the inorganic network at 500 °C). Figure 1 presents the XPS spectra. The Si 2p spectrum in [Fig.lA] shows the Si binding energies at 103 and 102.3 eV attributed to Si typical of SiO2 and Si-Li, respectively. [Fig.lB] presents the Ois spectrum which shows two main components attributed to Li2SiO3 and SiO2 at 530.2 and 532 eV, respectively. It is specified that the 532 eV component also includes the PEO-bound C-O. To be sure of the contribution of PEO-bound C-O, the samples were calcined for 2 h at 550 °C to remove the organic fraction ( [Fig.lC] and [Fig.lD]). XPS analysis reveals a strong decrease in the intensity of the 532 eV component, which is now in the range of the 530 eV Li2SiO3 intensity. This decrease in the 532 eV component intensity confirms the suppression of the PEO-bound C-O contribution by the calcination process.. XPS analysis of the calcined sample allows highlighting the contributions of chemical environments in the solid electrolyte. By removing the C-O contribution from PEO through calcination, not only the oxygen contribution of SiO2 can be amplified and compared to that of Li2SiO3, but also the two oxides SiO2 and Li2SiO3 can be distinctly identified. Thus, the inorganic network within the polymer matrix, responsible for the improvement of mechanical properties, consists of two distinct oxides: SiO2 and Li2SiO3.

[0189] The stability of the solid electrolyte was studied by thermogravimetric analysis (TGA). [Fig.2] shows the thermograms of the solid electrolytes with different amounts of theoretical silica: 5 wt% (curve A), 10 wt% (curve B), 15 wt% (curve C) and 20 wt% (curve D). The percentage of solid residues for each sample corresponds to the theoretical amounts of silica in the initial samples: 4 wt%, 8 wt%, 13 wt% and 19 wt%, respectively. For all thermograms, degradation occurred above 240 °C, indicating that the solid electrolytes are stable up to 240 °C, even with the lowest amount of silica (5 wt%).

[0190] To evaluate the potential of solid electrolyte in the application of electrochemistry, ionic conductivity, electrochemical stability, influence of silica and lithium salt amounts were studied. All these results are shown in Figure 3.

[0191] [Fig.3A] illustrates the conductivity as a function of temperature for different amounts of silica. The Arrhenius diagram is shown for a temperature between 10 °C and 90 °C. These results show that the ionic conductivity decreases with the amount of silica that increases, the highest conductivity values ​​are obtained for the sample with the lowest amount of silica, i.e. 5% by weight, with a value around 10 4 S.cm1 at 30 °C. The conductivity of the solid electrolyte in situ has no significant change during the cycles of cooling on the conductivity measurement between 10°C and 90°C.

[0192] [Fig.3B] illustrates the ionic conductivity as a function of temperature for different salt contents for CPE_10%. The Arrhenius diagram is shown for a temperature between 10 °C and 90 °C. The conductivity values ​​decrease with salt content for lower temperatures, from 10 °C to 40 °C with a maximum conductivity at a molar ratio of ethylene oxide to LiTFSI of 20:1. For higher temperatures (above 50 °C), the amount of lithium salt has almost no effect on the conductivity. This is because the increased solubility of LiTFSI in PEO at high temperatures compensates for the loss of conductivity due to higher amounts of lithium salt.

[0193] [Fig.3C] presents the current-potential curves of PEO and CPE_10%. The electrochemical stability window of the in situ synthesized CPE_10% (CPE) and the virgin polymer (PEO) was determined by LSV (Linear Sweep Voltammetry) from 2.8 V to 6 V at 1 mVs'. Stainless steel and lithium (metal) serve as working and reference electrodes. A low current was observed up to 4 V vs Li / Li+ for the silica-free solid electrolyte (virgin polymer-PEO), which represents the oxidation and decomposition process of PEO. Thus, the in situ reaction improves the electrochemical stability window up to 5.3 V compared to Li / Li+, which is comparable, if not superior, to previously reported high-voltage solid polymer electrolytes obtained by in situ sol-gel reaction.

[0194] CONCLUSION

[0195] Thus, the synthesis of solid electrolyte by hydrolysis of inorganic precursors preferably of an alkoxymetalloid in the presence of a lithium alcoholate and / or a lithium alkoxy alcoholate for example TEOS in the presence of lithium tert-butoxide as catalyst and co-precursors and dopant leads to a solid electrolyte with an organic polymer comprising at least one side chain preferably of the PEO type, entirely amorphous with a hybrid silica network. The solid electrolyte consisting of silica and an alkali or alkaline-earth element, preferably consisting of lithium metasilicate (Li-Si bound) in the inorganic phase exhibits ionic conductivity in the absence of lithium salt, showing that the Li+ of the inorganic fraction is also involved in the Li+ transport process.Furthermore, the inorganic network is involved in reducing the crystallinity of the organic polymer preferably PEO, leading to a fully amorphous structure with an enhanced conductivity of 10 4 Scm 1 at 30 °C. Moreover, the presence of an inorganic moiety improves the electrochemical stability voltage window up to 5.2 V compared to Li / Li+.

[0196] The invention may be the subject of numerous variants and applications other than those described above. In particular, unless otherwise indicated, the various charac Structural and functional characteristics of each of the implementations described above should not be considered as combined and / or closely and / or inextricably linked to each other, but rather as mere juxtapositions. Furthermore, the structural and / or functional characteristics of the different embodiments described above may be subject in whole or in part to any different juxtaposition or any different combination.

Claims

Claims

1. Composition consisting essentially of at least one first inorganic precursor, at least one second inorganic precursor, said inorganic precursors being dispersed in at least one organic polymer, and of which: - The at least one first inorganic precursor is selected from the family of alkoxymetalloids of formula M-(ORi)n with n ranging from 1 to 4 and Ri selected from hydrogen, alkyl, aryl, and / or alkenyl group; and M a metalloid element, - The at least one second inorganic precursor is selected from X-(OR2)m or X-(R2)m with m ranging from 1 to 2, R2 selected from hydrogen, alkyl, aryl and / or alkenyl group and X an alkali or alkaline-earth element, and - The at least one organic polymer comprises at least one side chain.

2. Composition according to claim 1, characterized in that the at least one organic polymer is a star polymer.

3. Composition according to claim 1 or 2, characterized in that the at least one organic polymer is selected from polyoxide or co-polyoxide of alkylene(s), polymethacrylate, polyacrylate, polysaccharide, polyacrylonitrile, polyimide and / or (co)polymers of VF2 (for vinyldiene fluoride), their derivative and / or their mixture.

4. Composition according to one of the preceding claims, characterized in that the alkali or alkaline-earth element is selected from: Li, Na, K, Be and / or Mg.

5. Composition according to one of the preceding claims, characterized in that the metalloid element is selected from Si and / or B.

6. Composition according to one of the preceding claims, characterized in that it further comprises at least one salt, preferably one or more lithium salts.

7. Composition according to one of the preceding claims, characterized in that it further comprises inorganic particles.

8. Use of the composition according to one of the preceding claims for forming a solid electrolyte.

9. Solid electrolyte, characterized in that it comprises at least one inorganic network, having at least one alkali or alkaline-earth element, dispersed in at least one organic polymer, said inorganic network corresponding to a condensation between at least one first inorganic precursor and at least one second inorganic precursor, - The at least one first inorganic precursor is selected from the family of alkoxymetalloids of formula M-(ORi)n with n ranging from 1 to 4 and Ri selected from hydrogen, alkyl, aryl, and / or alkenyl group; and M a metalloid element, - The at least one second inorganic precursor is selected from X-(OR2)m or X-(R2)m with m ranging from 1 to 2, R2 selected from hydrogen, alkyl, aryl, and / or alkenyl group; and X an alkali or alkaline-earth element, and - The at least one organic polymer comprises at least one side chain.

10. Solid electrolyte according to claim 9, characterized in that the at least one organic polymer comprises a condensation of the at least one first inorganic precursor with the at least one second inorganic precursor in its hydrolyzed form to form an inorganic network, said inorganic network condensing with the at least one organic polymer to form an organic / inorganic hybrid network.

11. Film obtained from the composition according to any one of claims 1 to 7.

12. Use of a solid electrolyte according to one of claims 9 or 10 in electrochemical devices of the accumulator, battery, capacitor, electrochemical double-layer electric capacitor, membrane-electrode assembly (MEA) type for fuel cell or electrochromic device.

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