Hybrid solid electrolyte with reduced polymer / ceramic interfacial strength

Abstract

The present application relates to ceramic / polymer hybrid solid electrolytes with improved interfacial strength, comprising a surface-dehydrated pre-treated ceramic.

Description

[0001]DESCRIPTION TITLE: HYBRID SOLID ELECTROLYTE WITH REDUCED POLYMER / CERAMIC INTERFACIAL RESISTANCE The present invention relates to the field of batteries, and in particular to all-solid-state hybrid electrolyte batteries. Unlike flammable, liquid organic electrolytes, solid electrolytes represent promising candidates for the development of safer lithium metal and Li-ion batteries. Solid electrolytes can be of the solid polymer or ceramic type: Polymer-type electrolytes allow good contacts with active material particles and can be shaped by economical and automated solvent-free processes such as extrusion, but have low ionic conductivities. Ceramic-type electrolytes benefit from high ionic conductivity, but are limited by their poor ability to maintain intimate contacts with electrode materials.Hybrid (or composite) solid electrolytes combining ceramic and polymer electrolytes have been described by Keller et al, J. Power Sources, 2018, 392, 206-225. They represent a preferred development path. However, these electrolytes impose an organic / inorganic interface, the resistance of which must be minimized to optimize electrochemical performance. Chen et al ACS Energy Letters 2019, 4, 1080-1085 reports the contrasting effects of plasticizing polymers, such as TEGDME and DMC, on the interfacial resistance between polyethylene glycol (PEO, polyethylene oxide) and a LiCGC ceramic. Therefore, it remains to improve the interfacial resistance of hybrid solid electrolytes in order to accelerate the progress of all-solid technologies to envisage their industrialization with limited safety risks, while maintaining satisfactory conductivity and energy densities.It has now been discovered that the interfacial resistance can be reduced by appropriate treatment of the ceramic. According to a first object, the present invention relates to a hybrid solid electrolyte comprising a pre-treated oxide-type ceramic and an ionically conductive polymer, characterized in that the pre-treated ceramic is dehydrated on the surface. The invention therefore relates to a hybrid solid electrolyte, i.e. a solid polymer electrolyte (SPE) based on ceramic and polymer, the ceramic of which has undergone a desiccant pre-treatment before assembly with the polymer. According to the invention, the ceramic is of the oxide type. It can be chosen from lithium ionically conductive ceramics, and can in particular be chosen from ceramics of the Nasicon, Lisicon, Garnet, Perovskite families. More particularly, mention may be made of LATP, LAGP, LLTO, LLZO ceramics.These ceramics and their use in solid electrolytes are known from the literature. Thus, LATP denotes ceramics comprising Li, Al, Ti, P, and possibly other substitution elements such as Ge, Zr. Representative LATPs may have the formula Li1+xAlxTi2-x(PO4)3 (where 0 <x<1) et sont par exemple décrites par Thokchom, et al dans J. Power Sources, vol.195, p.870, 2010. Selon un mode de réalisation, la céramique LATP peut être une céramique de type Ohara LiCGC (Li2O−Al203−SiO2−P2O5−TiO2−GeO2). Elle est notamment disponible commercialement (Ohara corporation). LAGP désigne les céramiques à base de Li, Al, Ge et P, répondant notamment à la formule Li1+xAlxGe2-x(PO4)3 (où 0<x<1) LLZO désigne les céramiques à base de Li, La et O, telles que celle de formule Li7La3Zr2O12 décrites par Murugan et al dans Angew. Chem. Int. Ed., 46 (2007), p.7778. LLTO fait référence aux céramiques comprenant Li, La, Ti et O, telle que La. 0.57 Li 0.29TiO3 marketed by Toho Titanium Co Ltd. According to the invention, the ceramic is at least partially dehydrated on the surface, this partial dehydration being understood in relation to the native ceramic. The term "native ceramic" refers to the ceramic before pre-treatment, and refers in particular to commercially available ceramics, or to re-hydrated ceramics, for example ceramics that may have undergone a desiccant treatment but subsequently stored in conditions conducive to rehydration. In these native ceramics, a portion of the surface oxygen atoms is hydrated. Thus, these surface oxygen atoms, typically present in the (M- O) form, where M refers to a cation of the solid electrolyte, are at least partly in the form of hydroxyl functions (OH).The said cation M is a cation which constitutes in the structure of the inorganic solid electrolyte, the cationic network in interaction with the anionic framework constituted of oxygens ("0. 2-", bulk oxygen), These are generally cations of metals (Al, Sn, etc.), transition metals (Ti, Zr, Ta, etc.), alkali or alkaline earth, metaloid (Si, Ge) or non-metals (P). OM bonds refer to the iono-covalent bonds between oxygen and these cations at the heart of the structure (crystalline or glassy) of the solid, as opposed to the OH bonds that surface oxygens can form in equilibrium with their environment. These surface OH bonds represent a defect in the structure and give a signature that can be analyzed in the XPS response. Thus, these native ceramics can be defined by the atomic percentage of oxygen present in the surface hydroxyl functions %O(OH)i and by the atomic percentage of oxygen present in the surface oxide functions %O(MO)i, where M refers to the metal cation and i refers to the initial value of the native ceramic, i.e. before treatment.Said atomic percentages of oxygen can in particular be measured by XPS (X-ray induced photoelectron spectrometry). For these native ceramics, the %O(OH)i / %O(MO)i ratio is typically greater than 20%. The pre-treatment is said to be desiccant in that its function is to reduce the quantity of hydroxyl (OH) functions, i.e. to reduce the share of hydroxyl functions in favor of oxide functions. Thus, according to one embodiment, the pre-treated ceramics have a %O(OH) ratio. f / %O(MO) f, where f refers to the pre-treated ceramic, is typically less than 20%, in particular less than 15%. According to one embodiment, the ceramic may be pre-treated by a heat treatment, in particular at a temperature between 100 and 700°C, preferably between 200 and 400°C. According to an alternative, or cumulative, embodiment, the ceramic may be pre-treated by the action of a hydrophilic and polar solvent. Said solvent may also be aprotic. Typically, said solvent may be chosen from acetonitrile (ACN), dimethylformamide (DMF), dimethyl carbonate (DMC), methanol, isopropanol, dimethyl sulfoxide (DMSO), cyclohexane and sulfolane. Ionic polymer refers to the polymers conventionally used in solid polymer batteries. Typically the ionic polymer is chosen from (co)polymers based on ether, carbonate, nitrile, acetate, imine, or lactone, etc.Thus, mention may in particular be made of polyethylene oxide (PEO) or polycaprolactone (PCL), in particular PEO. According to one embodiment, the hybrid solid electrolyte may also comprise one or more additional ingredients, typically present in hybrid solid electrolytes. Mention may thus be made of the additional presence of a metal salt, in particular a lithium salt, such as LiTFSI (Lithium bis(trifluoromethanesulfonyl)imide), LiFSI (Lithium bis(fluorosulfonyl)imide), LiNO3 (lithium nitrate), LiBOB (Lithium bis(oxalato)borate), LiDFOB (lithium difluoro(oxalato)borate), LiPF6 (Lithium hexafluorophosphate), LiBF4 (lithium tetrafluoroborate), LiCF3SO3 (lithium triflate, LiTf), LiClO4 (lithium perchlorate) or a mixture of salts. When the ionic polymer has been prepared by solvent means, it may possibly include traces of residual solvent from its preparation process.Thus, according to one embodiment, the hybrid solid electrolyte according to the invention may comprise traces of residual solvent as an additional ingredient. According to another subject, the present invention also relates to the process for preparing a hybrid solid electrolyte according to the invention, said process comprising the steps of: - Desiccant pre-treatment of an oxide-type ceramic having an atomic percentage of oxygen in the hydroxyl functions %O(OH). i , so as to obtain a pre-treated ceramic having an atomic percentage of oxygen present in the surface hydroxyl functions %O(OH) f, said percentages being measured by XPS, and such that the %O(OH)f / %O(OH)i ratio is between 20 and 60%, and - Contacting the ceramic thus pre-treated with an ionic conductive polymer. According to one embodiment, the desiccant treatment may comprise heat treatment of the ceramic at a temperature between 100 and 700°C, preferably between 200 and 400°C. According to an alternative or cumulative embodiment, the desiccant pre-treatment may comprise contacting the ceramic with a hydrophilic and polar solvent. This may in particular be carried out by spraying the solvent onto the ceramic or immersing (or dipping) the ceramic in the solvent. According to either alternative, the method may further comprise the prior step of preparing the polymer by dry and / or solvent means. It is therefore understood that the ionic polymer may optionally comprise traces of residual solvent from its preparation process.Contacting means the assembly of the electrolyte by means of the pre-treated ceramic and the conductive polymer. According to one embodiment, this contacting step can be carried out by simple mixing of these two constituents, or by a sandwich-type assembly (two outer polymer layers encompassing an inner ceramic layer), or even according to a system with deposited polymer / ceramic / polymer layers). According to another object, the present invention also relates to a method for improving the interfacial resistance of a hybrid ceramic / polymer solid electrolyte such that the ceramic is of the oxide type and such that the polymer is ionically conductive, said method comprising: the preliminary desiccant treatment of said oxide-type ceramic having an atomic percentage of oxygen in the hydroxyl functions %O(OH). i, so as to obtain a pre-treated ceramic having an atomic percentage of oxygen present in the surface hydroxyl functions %O(OH) f , said percentages being measured by XPS, and such that the ratio %O(OH) f / %O(OH) iis between 20 and 60%, and the mixture of the ceramic thus pre-treated with the ionically conductive polymer. According to another object, the present invention also relates to an electrochemical element comprising a hybrid solid electrolyte according to the invention. The term "electrochemical element" means an elementary electrochemical cell consisting of the positive electrode / electrolyte / negative electrode assembly, operating as an accumulator, that is to say allowing the energy supplied by a chemical reaction to be transformed into a current. In solid-type elements, the electrolytic compounds may be included in the electrolytic layer, but may also be included partly within the electrodes.A solid element according to the invention is therefore made up of a negative electrode layer, a positive electrode layer and an electrolytic separating layer, such that the electrolyte particles according to the invention are present within at least one of the three layers. The electrochemical element according to the invention is particularly suitable for lithium accumulators, such as Li-ion, Li metal, primary Li (non-rechargeable) and Li-S accumulators. These materials can also be used in Na-ion, K-ion, or even Mg-ion or Ca-ion type accumulators. The negative electrode layer is typically made up of a conductive support used as a current collector on which the negative electrode material is deposited, comprising a negative electrode active material to which the solid electrolyte and an electronically conductive material can be added. A binder can also be incorporated into the mixture.The term "negative electrode" refers to when the accumulator is in discharge, the electrode functioning as an anode, the anode being defined as the electrode where an electrochemical oxidation reaction (emission of electrons) takes place. In the context of the present invention, the negative electrode can be of any known type. It is understood that in systems without anode called "anode free", a negative electrode is also present (generally initially limited to the current collector only). The negative electrode active material is not particularly limited. The positive electrode layer typically consists of a conductive support used as a current collector on which is deposited the positive electrode material comprising, in addition to the solid electrolyte, a positive electrode active material and a carbon-based electronic conductive material. A binder can also be incorporated into the mixture.This carbon additive is distributed in the electrode so as to form an electronic percolating network between all the particles of active material and the current collector. The term "positive electrode" refers to the electrode functioning as a cathode when the accumulator is discharging. In the context of the present invention, the positive electrode may be of any known type. The electronically conductive material is generally chosen from graphite, carbon black, acetylene black, soot, graphene, carbon nanotubes or fibers or a mixture thereof. A current collector is understood to mean an element such as a pad, plate, sheet or other, made of conductive material, connected to the positive or negative electrode, and ensuring the conduction of the flow of electrons between the electrode and the terminals of the battery.The current collector is preferably a two-dimensional conductive support such as a solid or perforated strip, made of metal, for example nickel, steel, stainless steel, or aluminum. According to another object, the present invention also relates to an electrochemical module comprising the stack of at least two elements according to the invention, each element being electrically connected to one or more other element(s). The term "module" therefore designates here the assembly of several electrochemical elements, said assemblies being able to be in series and / or parallel. According to another of these objects, the invention also relates to a battery comprising one or more modules according to the invention. The term "battery" means the assembly of one or more modules according to the invention. The invention preferably relates to accumulators whose capacity is greater than 100 mAh, typically 1 to 100 Ah.Figures [Fig 1] Figure 1 represents by squares the characteristic impedance spectrum recorded at 80°C for a reference PEO / LATP / PEO type system accompanied by the simulation (in solid line) by the software. [Fig 2] Figure 2 represents the comparison of the interfacial resistance of the LATP ceramic (LiCGC, Ohara) / polymer (PEO) hybrid electrolyte (normalized by the contact surface between the polymer and the ceramic), as a function of temperature, before and after pre-treatment with a desiccant polar solvent (acetonitrile (ACN), Dimethylformamide (DMF), DMSO, DMC, Isopropanol, Sulfolane): the curve represented by the solid squares represents the interfacial resistance of the electrolyte constituted by the “native ceramic” (0.5M) / PEO; the curve represented by the filled pentagons represents the interfacial resistance of an electrolyte consisting of the ceramic pre-treated in acetonitrile (ACN) (0.5M) / PEO; the lower curve represented by the open squares represents the interfacial resistance of an electrolyte consisting of the pre-treated ceramic in DMF (0.5M) / PEO; the curve represented by the solid triangles with the point facing upwards represents the interfacial resistance of an electrolyte consisting of the pre-treated ceramic in DMC (0.5M) / PEO; the curve represented by the open circles represents the interfacial resistance of an electrolyte consisting of the pre-treated ceramic in DMSO (0.5M) / PEO; the curve represented by the solid circles represents the interfacial resistance of an electrolyte consisting of the pre-treated ceramic in Sulfolane (0.5M) / PEO; the curve represented by the empty triangles with the point facing downwards represents the interfacial resistance of an electrolyte consisting of the ceramic pre-treated in Isopropanol (0.5M) / PEO; [Fig 3] Figure 3 represents the interfacial resistance of the LATP (LiCGC, Ohara) / polymer (PEO) ceramic hybrid electrolyte, as a function of storage time, when the ceramic was pre-treated with desiccant solvents. The legend is the same as that of Figure 2. [Fig 4] Figure 4 represents the comparison of the interfacial resistance of the LLZO / polymer (PEO) ceramic hybrid electrolyte, as a function of temperature, before (squares) and after cyclohexane pre-treatment (circles). [Fig 5] Figure 5 represents the comparison of the interfacial resistance of the LATP (LiCGC, Ohara) / polymer (PEO) ceramic hybrid electrolyte, as a function of temperature, before and after thermal pre-treatment of the ceramic. The curve represented by the solid squares represents the interfacial resistance of the electrolyte constituted by the “native ceramic” (0.5M) / PEO; the curve represented by the open hexagons represents the interfacial resistance of an electrolyte consisting of the ceramic pre-treated heat for a period of 12 hours (0.5M) / PEO; the curve represented by the solid stars represents the interfacial resistance of an electrolyte consisting of the ceramic pre-treated heat for a period of 72 hours (0.5M) / PEO; [Fig 6] Figure 6 represents the interfacial resistance of the LATP (LiCGC, Ohara) / polymer (PEO) ceramic hybrid electrolyte, as a function of storage time, when the ceramic has been pre-treated either by a solvent or thermally. The legend is similar to Figures 2 and 3.Examples In order to measure the interface resistance between the polymer (containing a lithium salt) and the ceramic, the polymer electrolyte was previously prepared as follows: The preparation takes place in a glove box with a controlled atmosphere for water and oxygen content (<1 ppm H2O and <5 ppm O2). The PEO polymer powder (100 kg / mol) is mixed with the lithium salt LiTFSI in a proportion corresponding to a salt concentration of 0.5M (mol.dm. -3) and the whole is heated to 80°C under regular stirring. Using a heating press, the mixture is hot pressed (70°C) in order to obtain a membrane in which polymer discs are cut. On the other hand, the ceramic (LATP or LLZO) is pre-treated using two methods: i) it is either previously immersed in a polar solvent (here ACN, DMSO, DMC, sulfolane, isopropanol, DMF) for 1 min then the excess solvent is removed using an absorbent cloth, and left in the glove box overnight before being used for measurement. ii) The second method consists of placing the ceramic in a sealed ampoule (Buchi) under secondary vacuum and heated to 200°C for one to three days before transferring it to the glove box. The cell for measuring the interface resistance between the polymer and the ceramic consists of a button cell composed of two stainless steel wedges between which is a polymer / ceramic / polymer sandwich.The latter is achieved by hot pressing two discs of polymer membranes onto the two stainless steel shims using a cover to delimit the contact surface of the polymer before placing a piece of ceramic between the two shims. The button cell is finally closed / sealed tightly and placed in a climatic chamber. The measurement of the interfacial resistance is enabled by measuring the impedance of the cell in a frequency range from 7 MHz to 100 mHz using a potentiostat (VMP300 Biologic) at different temperatures. Finally, the analysis of the impedance spectrum of the cell reveals a resistive contribution in the medium frequency domain which corresponds to the desired quantity (i.e.) the interfacial resistance. The latter can be extracted using software (Zview) by injecting an equivalent electrical diagram taking into account all the contributions present in the impedance spectrum (inserted in Figure 1).The characteristic impedance spectrum recorded at 80°C for a reference PEO / LATP / PEO type system accompanied by the simulation (solid line) by the software is represented in Figure 1 represented by squares (experimental points). Furthermore, the evolution of the interfacial resistance as a function of temperature is often represented in an Arrhenius representation (1 / Rint vs 1000 / T) which gives access to the activation energy of the reaction (i.e.) the slope of the curve. The following systems were studied: NB: the term "pristine" used here refers to the commercial ceramic, used as is, without prior treatment. It is therefore used as a reference, and illustrates the ceramic designated here as "native".^ PEO / LATP system (LiCGC, Ohara): ^ PEO / LATP pristine interface (Reference) ^ PEO / LATP interface pretreated in DMF ^ PEO / LATP interface pretreated in ACN ^ PEO / LATP interface pretreated thermally (12h @ 200°C) ^ PEO / LATP interface pretreated in DMSO ^ PEO / LATP interface pretreated in DMC ^ PEO / LATP interface pretreated in Isopropanol ^ PEO / LATP interface pretreated in Sulfolane ^ PEO / LATP interface pretreated thermally +++ (72h @ 200°C) ^ PEO / LLZO system (Li7La3Zr2O12, marketed by Toshima Mfg Co, Ltd): ^ PEO / LLZO pristine interface (Reference) ^ PEO / LLZO interface pretreated in cyclohexane ^ • XPS measurements: ^ LATP pristine (Reference) ^ LATP pretreated in DMF ^ LATP pretreated in ACN The initial values ​​(Interface resistance measured 1-2h after cell assembly) are shown in Figure 2 in the case of LATP ceramic (LiCGC). [Table 1]. Comments: The interface resistance is reduced when the ceramic is pre-treated in a solvent. The greatest decrease is observed in the case of DMC and ACN solvent. The final values ​​(Interface resistance measured several months after cell assembly) are shown in Figure 2 and Figure 3. Over time, the interface resistances continue to decrease and seem to tend towards the same limiting value of the order of [20-40 Ω.cm²]. [Table 2] o LLZO / PEO system The initial values ​​(Interface resistance measured 1-2h after cell assembly) are shown in Figure 4. Comments: In the case of LLZO ceramic, the interface resistance decreases sharply in the case of cyclohexane. ^ 200°C pretreatment of the ceramic o LATP / PEO system The initial values ​​(Interface resistance measured 1-2h after cell assembly) are shown in Figure 5. [Table 3] Comments: Heat treatment of ceramics is also an effective way to reduce interface resistance. It can be noted that when the pretreatment time is extended, the decrease in resistance is greater. The final values ​​(Interface resistance measured several months after cell assembly) are shown in Figure 6. [Table 4] Over time, the interface resistances decrease (with different kinetics) and tend towards the same limit value of the order of [20-30 Ω.cm²]. It can be noted that the heat treatment at 200°C for 72 hours allows to be very close to this value from the beginning. General conclusions: In the case of a PEO / LATP type system, the pretreatment of the ceramic (solvent or thermal) is a way to significantly reduce the interface resistance. As for the PEO / LLZO system, the interface resistance also decreases when the ceramic is pretreated in cyclohexane. In the present study, the reference system comprising a native ceramic presents higher interface resistance values ​​than all those recorded in the case of pre-treated ceramics (by a solvent or thermally).The lowest interface resistance was recorded in the case of a ceramic pre-treated heat for 72 hours for which the interface resistance was divided by a factor of 16 compared to the reference system. In the case of pre-treatment of the ceramic with solvent, the interface resistance was divided by a factor of 7 for the ACN and DMC solvents. Table 5 below shows the measurement of the chemical composition of the ceramic surface using the XPS technique, when the ceramic was pre-treated with a solvent and that of the "native" ceramic. [Table 5].

Claims

CLAIMS 1. Hybrid solid electrolyte comprising a pre-treated oxide ceramic and an ionically conductive polymer, characterized in that the pre-treated ceramic is surface dehydrated.

2. Hybrid solid electrolyte according to claim 1 such that said pre-treated ceramic has a ratio of the atomic percentage of oxygen present in the surface hydroxyl functions relative to the atomic percentage of oxygen present in the surface oxide functions %O(OH)f / %O(MO)f of less than 20%, in particular less than 15%, said percentages being measured by XPS (X-ray induced photoelectron spectrometry).

3. Hybrid solid electrolyte according to claim 1 or 2 such that said ceramic before pre-treatment has a ratio of the atomic percentage of oxygen present in the surface hydroxyl functions relative to the atomic percentage of oxygen present in the surface oxide functions %O(OH)i / %O(MO)i of greater than 20%. 4.Hybrid solid electrolyte according to any one of claims 1 to 3 such that the ceramic is pre-treated by heat treatment.

5. Hybrid solid electrolyte according to any one of claims 1 to 4 such that the ceramic is pre-treated by the action of a hydrophilic and polar solvent.

6. Hybrid solid electrolyte according to claim 5 such that said solvent is chosen from acetonitrile (ACN), dimethylformamide (DMF), dimethyl carbonate (DMC), methanol, isopropanol, dimethyl sulfoxide (DMSO), cyclohexane and sulfolane.

7. Hybrid solid electrolyte according to any one of the preceding claims such that the oxide type ceramic is chosen from ceramics of the Nasicon, Lisicon, Garnet, Perovskite families.

8. Hybrid solid electrolyte according to any one of the preceding claims such that the oxide ceramic is chosen from LiCGC, LATP, LAGP, LLTO, LLZO.

9. Hybrid solid electrolyte according to any one of the preceding claims such that the ionic polymer is chosen from PEO, ether-based (co)polymers, carbonate, nitrile, acetate, imine, or lactone.

10. Hybrid solid electrolyte according to any one of the preceding claims such that it further contains a metal salt. 11.A hybrid solid electrolyte according to claim 10 such that the metal salt is a lithium salt, such as LiTFSI (Lithium bis(trifluoromethanesulfonyl)imide), LiFSI (Lithium bis(fluorosulfonyl)imide), LiNO3 (lithium nitrate), LiBOB (Lithium bis(oxalato)borate), LiDFOB (lithium difluoro(oxalato)borate), LiPF6 (Lithium hexafluorophosphate), LiBF4 (lithium tetrafluoroborate), LiCF3SO3 (lithium triflate, LiTf), LiClO4 (lithium perchlorate) or a mixture of salts. 12.

13. A method for preparing a hybrid solid electrolyte according to any one of claims 1 to 11 comprising the steps of: - Desiccant pre-treatment of an oxide-type ceramic having an atomic percentage of oxygen in the hydroxyl functions %O(OH)i, so as to obtain a pre-treated ceramic having an atomic percentage of oxygen present in the surface hydroxyl functions %O(OH)f, said percentages being measured by XPS, and such that the ratio %O(OH)f / %O(OH)i is between 20 and 60%, and - Contacting the ceramic thus pre-treated with an ionically conductive polymer.

13. A method according to claim 12 such that the desiccant treatment comprises the heat treatment of the ceramic at a temperature between 100 and 700°C, preferably between 200 and 400°C.

14. A method according to claim 12 or 13 such that the desiccant pre-treatment comprises immersing the ceramic in a hydrophilic and polar solvent.

15. Method according to any one of claims 12 to 14 comprising the prior step of preparing the polymer by dry and / or solvent route.

16. Method for improving the interfacial resistance of a ceramic / polymer hybrid solid electrolyte such that the ceramic is of oxide type and such that the polymer is ionically conductive, said method comprising: the prior desiccant treatment of said oxide type ceramic having an atomic percentage of oxygen in the hydroxyl functions %O(OH) i , so as to obtain a pre-treated ceramic having an atomic percentage of oxygen present in the surface hydroxyl functions %O(OH) f , said percentages being measured by XPS, and such that the ratio %O(OH) f / %O(OH) iis between 20 and 60%, and the mixture of the ceramic thus pre-treated with the ionically conductive polymer.

17. Electrochemical element comprising a hybrid solid electrolyte according to any one of claims 1 to 11.

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