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    • 专利摘要:
    The present invention relates to thermotropic ionic liquid crystal molecules, comprising a so-called rigid part, a so-called flexible portion covalently bonded, directly or via a spacer, to said rigid part, and one or more ionic groups covalently bonded to said part. rigid.
    公开号:FR3041358A1
    申请号:FR1558864
    申请日:2015-09-21
    公开日:2017-03-24
    发明作者:Lionel Picard；Gerard Gebel；Melody Leclere；Hakima Mendil；Patrice Rannou
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    The present invention relates to novel compounds that can be used as electrolytes, especially in electrochemical generation or storage systems.
    Such electrolytes can be used in various electrochemical systems or devices, especially in lithium batteries. In a conventional manner, the operating principle of an electrochemical generator is based on the insertion and removal, also called "uninsertion", of an alkali metal ion or a proton, in and from the positive electrode. , and depositing or extracting this ion, on and from the negative electrode.
    The main systems use lithium cation as an ionic transport species. In the case of a lithium battery for example, the lithium cation extracted from the cathode during charging of the battery is deposited on the anode, and conversely, it is removed from the anode to be inserted in the the cathode during the discharge.
    The transport of the proton or the alkaline or alkaline earth metal cation, in particular the lithium cation, between the cathode and the anode is provided by an ionic conductive electrolyte.
    The formulation of the electrolyte used is essential for the performance of the electrochemical system, particularly when it is used at very low or very high temperatures. The ionic conductivity of the electrolyte conditions in particular the efficiency of the electrochemical system since it affects the mobility of the ions between the positive and negative electrodes. Other parameters are also involved in the choice of the electrolyte used. These include its thermal, chemical or electrochemical stability in the electrochemical system, as well as economic, safety and environmental criteria, including in particular the toxicity of the electrolyte. In general, the electrolytes of the electrochemical systems are in liquid, gelled or solid form.
    With regard to the electrolytes in liquid form, the conventional electrolytes of electrochemical generators with a metal cation of one of the first two columns of the periodic table of the elements, for example lithium, are composed of a salt of this cation dissolved in an organic or aqueous medium (typically in carbonate solvents, acetonitrile for lithium batteries), in the presence or absence of additives.
    For example, conventional supercapacity electrolytes are composed of an organic salt (typically a tetraethylammonium tetrafluoroborate salt Et4N-BF4) dissolved in acetonitrile.
    Their use as a complete electrochemical storage system, for example in a Li-ion battery, however, requires the addition of a separator to ensure electrical isolation between the positive and negative electrodes. Also, even if these electrolytes have good ionic conductivities, they nevertheless pose safety and cost problems in the context of the use of organic solvents (low thermal stability), and electrochemical stability in the context of the implementation of of an aqueous medium.
    As regards gelled electrolytes, these are liquid electrolytes, for example as described above, trapped in a "host" polymer. The solvent (s) of the liquid electrolyte must have an affinity with the host polymer, neither too high (solubilization of the polymer) nor too low (exudation). The host polymer must allow maximum incorporation of liquid while retaining mechanical properties to ensure physical separation between the two electrodes.
    Finally, to address the safety issues related to the presence of the solvent, it has been proposed to implement solid polymeric electrolytes. These polymers entering the composition of the electrolyte must have good ionic conduction properties in order to be used satisfactorily in electrochemical generation and storage systems.
    It is for example known to use as polymer electrolytes that do not require the use of a separator, POE poly (oxyethylene) in which is dissolved an alkali metal or alkaline earth metal salt (depending on the chemistry of the electrodes). However, these electrolytes have limited ionic conductivity performance related to the cation transport mechanism, called "assisted", and require a high temperature of use (60 ° C to 80 ° C). The polymers are thus conductive in a gelled physical state.
    The electrolyte membrane of electrochemical generator systems of the proton exchange membrane type fuel cell type, conventionally constituted by a carbofluorinated main chain polymer bearing pendant groups comprising sulphonic acid functional groups, may also be mentioned as the polymer electrolyte. such as Nafion®. At present, the use of this type of polymer for proton conduction requires, however, to control the hydration rate of the membrane to obtain the desired performance. This type of polymer is a semi-crystalline polymer, of which only the amorphous part has conductive properties, the crystalline part conferring the mechanical properties necessary for its proper functioning in complete system.
    Various studies have been conducted to increase the ionic conduction performance of polymer electrolytes.
    For example, the international application WO 00/05774 describes phase-separated micro-phase block copolymers consisting of a first ion-conductive block, for example of polyethylene oxide, and a second block, non-conductive and non-conductive. miscible with the first block to ensure a micro-phase separation, for example of polyalkylacrylate or polydimethylsiloxane type. These polymeric electrolytes do not require the addition of an additional salt since an anion (for example carboxylate, sulfonate or phosphate) is immobilized on the polymer. It has also been proposed to mix a polystyrene bearing sulfonyl (trifluoromethylsulfonyl) imide and POE groups to produce an electrolyte membrane (Meziane et al., Electrochimica Acta, 2011, 57, 14-19). These polymer electrolytes nevertheless have insufficient ionic conductivities, of the order of 9.5 × 10 -6 S / cm at 70 ° C. In addition, it is not possible for most current application areas to implement operating temperatures above 70 ° C.
    Finally, it is also possible to cite the document FR 2 979 630 which proposes a solid electrolyte of type B-type triblock copolymer type or BAB type tri-block copolymer, with A an unsubstituted polyoxyethylene chain and B an anionic polymer formed from one or more vinyl-type monomers and derivatives substituted with a sulfonyl (trifluoromethylsulfonyl) imide anion (TFSI). The maximum conductivity, of the order of 10-5 S / cm, is obtained at 60 ° C with a polymer comprising 78% by weight of POE.
    For obvious reasons, improving electrolyte performance is an ongoing goal.
    There remains therefore a need for an electrolyte having a high ionic conductivity and preferably having a transport number closest to the possible unit.
    There is also a need for an electrolyte having improved electrochemical stability, especially over an extended temperature range.
    The present invention aims precisely to propose new electrolytes, ionic, cationic or protonic conductors, having improved ionic conductivity and electrochemical stability.
    More particularly, it relates, according to a first of its aspects, to a thermotropic ionic liquid crystal molecule comprising: • a so-called rigid part, consisting of a polycyclic group Ar formed from two to six rings of which at least one is aromatic, said rings comprising, independently of each other, from 4 to 6 members, said polycyclic group being able to include up to 18 heteroatoms, in particular selected from the group consisting of S, N and O; A part, said flexible, formed of one or more linear or branched, saturated or unsaturated, fluorinated or non-fluorinated aliphatic chains, the said chain or chains being optionally interrupted by one or more heteroatoms, by one or more metalloids and / or by one or more (hetero) rings, aromatic or otherwise, of 4 to 6 members, and optionally substituted with one or more groups selected from the group consisting of hydroxyl, -NH 2 and oxo; said flexible portion being covalently bonded, directly or via a spacer, to said rigid portion; and one or more ionic groups -AX "CX +, -Ax" being an anionic group covalently bonded to said rigid portion, with x being equal to 1 or 2, -Ax 'being selected from the group consisting of sulfonate anions, sulfonylimide of formula -SO2-N'-SO2CyF2y + i with y integer ranging from 0 to 4, borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulphide, selenate, nitrate and perchlorate; and
    Cx + being a counter-cation of the anionic group -Ax ', selected from the group consisting of H + and the cations of alkali and alkaline earth metals.
    A thermotropic liquid crystal is defined by three types of successive states, which it assumes as a function of temperature.
    Below its melting temperature, it is in a crystalline state (or crystalline phase). Then, beyond its melting temperature, it passes into a mesomorphic state consisting of a mesophase or a succession of mesophases. Finally, beyond its clarification temperature, it goes into an isotropic state (or amorphous phase).
    By "melting temperature" is meant the temperature at which a thermotropic liquid crystal changes from a crystalline state to a mesomorphic state.
    By "clarification temperature" is meant the temperature at which a thermotropic liquid crystal leaves its mesophase or last mesophase from a succession of mesophases to enter an isotropic (or liquid) state.
    By "mesomorphic state" is meant the state in which a thermotropic liquid crystal is located when it is heated to a temperature above its melting point and below its clarification temperature.
    By "ionic liquid crystal" is meant a liquid crystal carrying at least one ionic group, called -AX'CX +.
    As illustrated in the examples which follow, the inventors have shown that, when the thermotropic ionic liquid crystal molecules of the invention are in a mesomorphous state, these have an ionic conductivity (cationic or anionic) or protonic.
    The temperature range in which a thermotropic liquid crystal molecule is in a mesomorphic state can be determined by a method known to those skilled in the art, such as DSC (Differential Scanning Calorimetry or Differential Scanning Calorimetry).
    This method of characterization also makes it possible to measure the melting and clarification temperatures.
    The nature of the mesophases of a mesomorphic state can be determined by a combination of other characterizations such as MOP (Optical Microscope in Polarized Light), XRD (X-ray Diffraction) and / or SAXS ("Small Angle X"). -ray Scattering "or X-ray scattering at small angles), the latter being generally used in addition to the DRX.
    Thus, according to another of its aspects, the invention relates to the use of a thermotropic ionic liquid crystal molecule as defined above, in a mesomorphous state, as an electrolyte in an electrochemical system. The invention also relates to an electrolyte comprising, or even being formed, thermotropic ionic liquid crystal molecules as defined above, in a mesomorphous state.
    The molecules according to the invention can be used as electrolytes in many electrochemical systems, such as generators, for example lithium batteries, and electrochemical conversion systems, for example proton exchange membrane fuel cells ( PEMFC).
    The use of the molecules according to the invention as electrolytes proves to be advantageous for several reasons.
    Firstly, since these molecules are ionically conductive in a mesomorphic state, they have a temperature of use as a strongly enlarged electrolyte, which may be in the entire temperature range in which the molecules are in a mesomorphic state, which generally corresponds to the temperature range between the melting temperature and the clarification temperature. The molecules of the invention may further be ionically conductive at a temperature above their clarification temperature.
    An electrochemical system, for example a lithium battery, made from an electrolyte according to the invention can thus operate over a wide temperature range, preferably from -60 ° C. to + 300 ° C., and more preferably between -20 ° C and +200 ° C.
    Furthermore, the ionic conductivity of an electrolyte according to the invention is based on a "direct" conduction mechanism, by "jump" ("hopping" in English) of the Cx + cations of an anionic group-Ax ', located on a polycyclic group Ar, to the other, and not on an assisted mechanism as is the case for example of the polymer electrolytes proposed by Cohen et al. Molecular Transport in Liquids and Glasses, J. Chem. Phys. 31, 1164 (1959). Without wishing to be bound to a particular theory, this mechanism is enabled by the arrangement of the molecules of the invention in a mesomorphic state.
    An electrolyte according to the invention thus leads to improved performances in terms of ionic, protonic or cationic conductivity. Other characteristics, variants and advantages of the molecules and electrolytes according to the invention, their preparation and their implementation will emerge more clearly on reading the description, examples and figures which will follow, given for illustrative and non-limiting purposes. of the invention.
    In the remainder of the text, the expressions "between ... and ...", "ranging from ... to ..." and "varying from ... to ..." are equivalent and mean to mean that terminals are included unless otherwise stated.
    Unless otherwise indicated, the expression "comprising / including a" shall be understood as "comprising / including at least one".
    MOLECULES OF THE INVENTION
    As mentioned above, the thermotropic ionic liquid crystal molecules according to the invention comprise: • a so-called rigid part, consisting of a polycyclic group Ar formed from two to six rings of which at least one is aromatic, said rings comprising, independently each other, of 4 to 6 members, said polycyclic group may include up to 18 heteroatoms, in particular selected from the group consisting of S, N and O; A part, said flexible, formed of one or more linear or branched, saturated or unsaturated, fluorinated or non-fluorinated aliphatic chains, the said chain or chains being optionally interrupted by one or more heteroatoms, by one or more metalloids and / or by one or more (hetero) rings, aromatic or otherwise, of 4 to 6 members, and optionally substituted with one or more groups selected from the group consisting of hydroxyl, -NH 2 and oxo; said flexible portion being covalently bonded, directly or via a spacer, to said rigid portion; and one or more ionic groups -AX'CX +, -Ax 'being an anionic group covalently attached to said rigid portion, with x being equal to 1 or 2, -Ax "being selected from the group consisting of sulfonate anions, sulfonylimide of the type -SO2-N'-SO2CyF2y + i with y integer ranging from 0 to 4, borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulphide, selenate, nitrate and perchlorate, and
    Cx + being a counter-cation of the anionic group -Ax 'selected from the group consisting of H1 and the cations of the alkali and alkaline earth metals.
    In the context of the invention, the term "alkyl" means a saturated, linear or branched aliphatic group; for example a C 1-4 -alkyl represents a carbon chain of 1 to 4 carbon atoms, linear or branched, more particularly a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl; "(Hetero) aromatic or non-aromatic ring of 4 to 6 members" means an unsaturated, partially saturated or saturated cyclic group with 4, 5 or 6 members, optionally comprising one or more heteroatoms, in particular chosen from the group consisting of oxygen, sulfur and nitrogen. An aromatic ring may especially be benzene; - "polycyclic group" means a group having two or more rings (rings) fused (ortho-fused or ortho- and peri-condensed) to each other, that is, presenting, in pairs, at least two carbons in common.
    In particular, a polycyclic group according to the invention is formed from two to six rings, the rings comprising, independently of each other, from 4 to 6 members.
    The polycyclic group may include one or more heteroatoms. This is called "polyheterocyclic grouping". "Alkali metals", the chemical elements of the first column of the periodic table of the elements, and more particularly chosen from the group consisting of lithium, sodium, potassium, rubidium, and cesium. Preferably, the alkali metal is lithium, sodium or potassium, and more preferably lithium; "Alkaline earth metals", the chemical elements of the second column of the periodic table of the elements, and more particularly chosen from the group consisting of beryllium, magnesium, calcium, strontium, barium and radium. Preferably, the alkaline earth metal is magnesium or potassium; - "metalloids" means the following chemical elements; boron, silicon, germanium, arsenic, antimony, tellurium, and asiat. Preferably, the metalloid is boron or silicon; - "spacer", an atom or a group of valence atoms at least equal to 2, covalently connecting the rigid portion and the flexible portion. Preferably, the spacer connects the rigid portion to at least two, preferably two, aliphatic chains of the flexible portion. Preferably, the spacer is a divalent or trivalent atom, advantageously trivalent. As suitable spacer, there may be mentioned nitrogen, oxygen, phosphorus, and sulfur.
    Rigid part
    Ar is a polycyclic group comprising from 2 to 6 rings having from 4 to 6 members, preferably from 2 to 4 rings, at least one of the rings being aromatic and preferably representing a benzene ring.
    According to a variant, Ar is an aromatic polycyclic group formed from 2 to 6 fused aromatic rings with 6 members, preferably from 2 to 6 fused benzene cycles, advantageously from 2 to 4 fused benzene cycles.
    More particularly, Ar may have one of the following polycyclic skeletons:
    It is understood that the Ar group may be a polyheterocyclic group having one of the skeletons presented above in which one or more carbon atoms are replaced by one or more heteroatoms, in particular chosen from the group consisting of S, N and O .
    According to a particular embodiment, Ar is an aromatic bicyclic group, in particular having an aromatic naphthalene backbone.
    Preferably, Ar is a naphthalene group.
    Flexible part
    Preferably, the aliphatic chain or chains of the flexible part comprise from 4 to 18 carbon atoms.
    Preferably, the aliphatic chain or chains of the flexible part is (are) substituted by at least one or even one hydroxyl group.
    According to one embodiment, the flexible portion is formed of: a single branched aliphatic chain, having a linear sequence of at least 6 covalent bonds; or - at least two linear or branched aliphatic chains, each of the chains having a linear sequence of at least 6 covalent bonds.
    According to a particular embodiment, each of the aliphatic chains is formed of a single segment or of a linear sequence of at least two chain segments, in particular of two or three chain segments of different chemical nature.
    Preferably, each of the aliphatic chains represents a linear alkyl chain comprising from 6 to 18 carbon atoms, preferably from 6 to 12 carbon atoms, optionally fluorinated, optionally substituted with at least one or even one hydroxyl group, and optionally interspersed with by one or more oxygen atoms.
    According to one variant, said at least one aliphatic chain (s) forming said flexible part is / are covalently bonded directly to one or more carbon atoms or heteroatoms of the Ar group forming the rigid part.
    In this variant, a heteroatom preferably designates a nitrogen atom.
    According to another variant, said one or more aliphatic chain (s) forming said flexible part is / are covalently linked via a spacer to one or more carbon atoms or heteroatoms of the Ar group forming the rigid part.
    In this variant, a heteroatom preferably designates a nitrogen atom.
    When the flexible part is formed of at least two aliphatic chains, these are preferably covalently bonded via a single spacer to the same carbon atom of the Ar group forming the rigid part.
    When the flexible part is formed of two aliphatic chains, these are preferably covalently linked via a single trivalent spacer to the same carbon atom of the Ar group forming the rigid part.
    According to this variant, said at least one aliphatic chain (s) forming said flexible part is / are preferably covalently bonded to a carbon atom of the Ar group via a valence atom greater than or equal to 2, in particular via a nitrogen atom.
    Said valence atom greater than or equal to 2, in particular said nitrogen atom, acts as a spacer covalently connecting said at least one aliphatic chain (s) forming said flexible part and the Ar group forming the rigid part. .
    When the flexible part is formed of at least two aliphatic chains, these are preferably covalently bonded to the same carbon atom of the Ar group forming the rigid part via a single valence atom greater than or equal to 2.
    When the flexible part is formed of two aliphatic chains, they are preferably covalently bonded to the same carbon atom of the Ar group forming the rigid part via a single valence atom equal to 2, in particular via a single atom of 'nitrogen.
    According to a particular embodiment, the flexible portion is formed of two linear alkyl chains, identical or different, preferably identical, comprising from 4 to 18 carbon atoms, preferably from 6 to 16 carbon atoms, optionally substituted with one or a plurality of hydroxyl groups, optionally interspersed with one or more oxygen atoms, said chains being bonded to a carbon atom of the Ar group via a nitrogen atom, preferably to the same carbon atom of the Ar group via a single atom of nitrogen.
    According to a preferred embodiment, the flexible portion is formed of two linear alkyl chains, comprising from 6 to 16 carbon atoms, each being substituted by a hydroxyl group and optionally interspersed with an oxygen atom, said chains being linked to a carbon atom of the Ar group via a nitrogen atom, preferably at the same carbon atom of the Ar group via a single nitrogen atom.
    Ionic group
    In the thermotropic ionic liquid crystal molecules of the invention, the anionic group -Ax 'may be more particularly chosen from the group consisting of sulphonate anions (of formula -SO3 ") and anions of formula -SO2-N-SO2-CyF2y + i with y varying from 0 to 4, preferably equal to 1.
    Preferably, -Ax 'is a sulfonate anion.
    Preferably, -Ax 'is an anion of formula -SO2-N "-SO2-CF3.
    According to an alternative embodiment of the invention, Cx + represents the H + proton.
    According to this variant, the -AX "CX + group preferably represents a group -S (VH +), where the sulfur atom is covalently bonded to a carbon atom or a heteroatom of the rigid part.
    As detailed in the rest of the text, such molecules can be advantageously used as electrolyte in a proton exchange membrane fuel cell (PEMFC) or a low temperature electrolyser.
    According to another variant embodiment of the invention, Cx + represents the Li + cation.
    According to this variant, the -AX "CX + group preferably represents a -SCh'LC group, where the sulfur atom is covalently bonded to a carbon atom or a heteroatom of the rigid part.
    As detailed in the rest of the text, such molecules can be advantageously used as electrolyte in a lithium battery.
    According to a particular embodiment, the molecules according to the invention have the following structure:
    in which -Ax "and Cx + are as defined above, and Ei and E2 represent aliphatic chains, identical or different, as defined above.
    Preferably, E 1 and E 2 represent identical aliphatic chains.
    Preferably, the general formula (I) corresponds to one of the two sub-formulas below:
    in which -Ax 'and Cx + are as defined above, and Ei and E2 represent aliphatic chains, identical or different, as defined above.
    According to a particular embodiment, the chains E 1 and E 2 represent linear chains, identical or different, comprising from 4 to 18 carbon atoms, preferably from 6 to 16 carbon atoms, optionally fluorinated, optionally substituted by one or more hydroxyl groups, optionally interspersed with one or more oxygen atoms.
    According to a preferred embodiment, the chains E 1 and E 2 represent linear chains, identical or different, comprising from 6 to 16 carbon atoms, each being substituted by a hydroxyl group, optionally fluorinated, and optionally interspersed with an atom of oxygen.
    The chains E 1 and E 2 preferably correspond to the general formula -CH 2 -CHOH-R, where R is a C 4 -C 18 alkyl group, optionally fluorinated, optionally interspersed with one or more oxygen atoms.
    Preferably, the thermotropic ionic liquid crystal molecules according to the invention are not polymers.
    Advantageously, the thermotropic ionic liquid crystal molecules according to the invention have a molecular mass less than or equal to 1500 g / mol, preferably less than 1000 g / mol.
    The thermotropic ionic liquid crystal molecules in accordance with the invention are particularly effective as electrolytes when the ratio by weight of the flexible part to the rigid part (excluding the ionic group or groups) is from 1/1 to 100/1, preferably from 1 to 100/1. / 1 to 50/1, advantageously 1/1 to 10/1.
    The subject of the present invention is in particular the following thermotropic ionic liquid crystal molecules, particularly suitable for use as an electrolyte:
    Preparation of the compounds of the invention
    The molecules according to the invention can be prepared by implementing nucleophilic substitution or addition methods known to those skilled in the art, as detailed below.
    The molecules of the invention may be prepared by bringing into contact, under conditions conducive to their interaction according to a substitution or nucleophilic addition reaction known to those skilled in the art, a precursor of the rigid part and a precursor of the flexible part.
    The precursor of the rigid part is advantageously carrying the ionic group (s) -AX'CX + or alternatively carrying one or more precursors of said ionic groups.
    According to one embodiment, the precursor of the rigid part carries a nucleophilic group, for example of the amine, hydroxyl or sulphide type, and the precursor of the flexible part carries an electrophilic group of epoxide or halogen type, isocyanate, nitrile, thiocarbonyl or carbonyl.
    Alternatively, the precursor of the flexible part carries a nucleophilic group, for example of the amine, hydroxyl or sulphide type, and the precursor of the rigid part carries an electrophilic group of epoxide, halogen, isocyanate or nitrile type, thiocarbonyl or carbonyl. As an illustration of the methods that a person skilled in the art can use to obtain the molecules of the invention, a method for preparing the molecules of the invention of formula (I) is described below and also in the examples which follow.
    The molecules of the invention of formula (I) can be prepared according to a process comprising at least the bringing into the presence of a compound having the following formula (F):
    with a precursor of the chain Ei and a precursor of the chain E2, said precursors being optionally identical when Ei and E2 are identical, under conditions conducive to their interaction according to a nucleophilic addition reaction.
    This reaction is preferably carried out in a polar aprotic solvent, such as dimethylformamide.
    This reaction is preferably carried out by heating the reaction mixture composed of the compound of formula (F), precursors and said solvent at a temperature of 80 ° C to 120 ° C.
    This reaction is preferably carried out in the presence of at least one equivalent of the precursor of the chain E 1 and at least one equivalent of the precursor of the chain E 2, relative to the compound of formula (F).
    The precursors of the chains E 1 and E 2 are advantageously carrying an electrophilic group of epoxide, halogen, isocyanate, nitrile, thiocarbonyl or carbonyl type, preferably of an epoxide group.
    The molecules of the invention of formula (I) in which E 1 and E 2 are identical may be obtained via a nucleophilic addition reaction between a compound of formula (I ') and a precursor of chains E 1 and E 2, carrying a group electrophilic, such as an epoxide group. This reaction is preferably carried out in the presence of at least two equivalents of the E1 and E2 chain precursor relative to the compound of formula (F).
    Of course, it is up to those skilled in the art to adjust the synthesis conditions to obtain the molecules according to the invention.
    Use as electrolyte
    The thermotropic ionic liquid crystal molecules according to the invention may advantageously be used, in a mesomorphous state, as an electrolyte in an electrochemical system.
    As mentioned above, a mesomorphic state refers to the mesophase or succession of mesophases in which the thermotropic ionic liquid crystal molecules according to the invention are in function of their temperature, situated between the melting temperature and the clarification temperature. The electrolyte formed of such molecules is advantageously used in combination with a porous separator on which said electrolyte is impregnated, said separator ensuring a physical separation between the two electrodes of the electrochemical system. As a separator, it is possible to use any porous separator conventionally used in an electrochemical system, such as, for example, a porous lithium battery separator or an ion exchange membrane of a fuel cell. The skilled person is able to choose a separator suitable for the implementation of the electrolyte.
    The thermotropic ionic liquid crystal molecules according to the invention in which Cx + represents a Li + cation may advantageously be used, in a mesomorphous state, as an electrolyte in a lithium battery.
    The thermotropic ionic liquid crystal molecules according to the invention in which Cx + represents H + can advantageously be used, in a mesomorphous state, as an electrolyte in a proton exchange membrane fuel cell, or a low temperature electrolyser.
    Electrolyte
    As mentioned above, the thermotropic ionic liquid crystal molecules according to the invention are ionic, protonic or cationic conductors, in their mesomorphous state.
    The present invention relates to an electrolyte comprising, or even being formed, thermotropic ionic liquid crystal molecules as defined above, in a mesomorphous state.
    In the electrolyte of the invention, the thermotropic ionic liquid crystal molecules are preferably used at a temperature of from 80 ° C. to 220 ° C., generally ranging from 100 ° C. to 200 ° C., preferably from 130 ° C. C at 170 ° C, for example of the order of 150 ° C.
    Preferably, the liquid electrolyte of the invention has a viscosity greater than or equal to 10 mPa.s, preferably from 100 mPa.s to 100 Pa.s at a temperature of between -60 ° C. and 300 ° C. .
    By "at a temperature between -60 ° C and 300 ° C" is meant that the liquid electrolyte of the invention has a viscosity as defined above at at least a temperature in this range. This does not necessarily mean that the liquid electrolyte of the invention has a viscosity as defined above at any temperature in this range.
    The viscosity can be measured by zero shear extrapolation of the viscosity versus shear rate curve at a given temperature, measured on a cone / plane or plane / plane viscometer / rheometer.
    This condition on the viscosity of the liquid electrolyte ensures good impregnation thereof in the separator of the electrochemical system. The electrolyte according to the invention has good properties of ionic conductivity.
    Preferably, the electrolyte of the invention has an ionic conductivity at 20 ° C. greater than or equal to 10 -9 S / cm, in particular between 10 -7 S / cm and 10 -5 S / cm, and an ionic conductivity. at 200 ° C greater than or equal to 10'5 S / cm.
    The ionic conductivity can be measured by electrochemical impedance spectroscopy in voltage or current, according to a method known to those skilled in the art.
    Electrochemical System The electrolyte according to the invention can be implemented in an electrochemical system, for example for a lithium battery.
    The present invention thus relates, according to yet another of its aspects, an electrochemical system comprising an electrolyte according to the invention.
    In the electrochemical system of the invention, the electrolyte is preferably impregnated on a porous separator as described above.
    The electrochemical system can be a generator, converter or electrochemical storage system. It may be more particularly a fuel cell, for example a proton exchange membrane fuel cell (PEMFC); a primary or secondary battery, for example a lithium, sodium, magnesium, potassium or calcium battery; a lithium-air or lithium-sulfur accumulator.
    According to a particular embodiment, the electrolyte is implemented in a battery, in particular a lithium battery.
    The present invention also relates, according to yet another of its aspects, a porous separator impregnated with an electrolyte according to the invention.
    Such a porous separator is particularly suitable for its implementation in an electrochemical system as described above. The invention will now be described by means of the following examples and figures, given of course by way of illustration and not limitation of the invention.
    Figure 1: Calorimetric analysis of the product 12-ANH by DSC under argon and with a heating rate of 10 ° K / min.
    Figure 2: Analysis of the product 12-ANH by DRX.
    Figure 3: Isotherms of sorption / desorption of water at 25 ° C of the product 12-ANH.
    Figure 4: Analysis of the product 12-ANH by S AXS, according to its hydration rate.
    Figure 5: Calorimetric analysis of the product 12-ANLi by DSC under argon and with a heating rate of 10 ° K / min.
    Figure 6: Analysis of the product 12-ANLi by DRX.
    Figure 7: Isotherms of sorption / desorption of water at 25 ° C of the product 12-ANLi.
    Figure 8: Analysis of ionic conductivity, ascent and descent of temperature, 12-ANLi and 14-ANLi products.
    FIG. 9: Analysis of ionic conductivity, in temperature rise, of the products 12-ANLi, 14-ANLi, 16-ANLi, 12-AN'Li and 16-AN'Li.
    EXAMPLES
    Preparation of synthetic intermediates
    Preparation of lithium 4-amino-1-naphthalenesulfonate (ANLi)
    1,340 g of 4-amino-1-naphthalenesulfonic acid (ANH) and 0.210 g of lithium hydroxide monohydrate (LiOH, H 2 O) were added in 20 ml of distilled water. The reaction medium was stirred overnight at room temperature. Excess ANH was removed by filtration. The filtrate was then concentrated by evaporation of the solvent under reduced pressure. After two washes with ethanol, a pink powder (ANLi) was obtained. 1H NMR (400 MHz, DMSO-d6, 300 K): δ ppm 7.89 (dd, 1H); 7.18 (dd, 1H); 6.83 (d, 1H); 6.52 (m, 2H); 5.68 (d, 1H); 4.96 (s, 2H). 13 C NMR (400 MHz, DMSO-d6, 300 K): δ ppm 146.11; 132.34; 130.61; 128.10; 126.45; 125.33; 123.56; 122.94; 122.26; 105.17.
    Preparation of lithium 5-amino-1-naphthalenesulfonate (AN'Lil
    24.441 g of 4-amino-1-naphthalenesulfonic acid (ANH) and 4,282 g of lithium hydroxide monohydrate (LiOH, H 2 O) were added in 500 ml of distilled water. The reaction medium was stirred overnight at room temperature. Excess ANH was removed by filtration. The filtrate was then concentrated by evaporation of the solvent under reduced pressure. After two washings with ethanol, a pink powder (AN'Li) was obtained.
    Example 1 Preparation of a 12-ANII Liquid Crystal According to the Invention
    2.0 g (8.96 mmol) of 4-amino-1-naphthalenesulfonic acid (ANH) and 3.29 g (17.9 mmol) of 1,2-epoxydodecane (ie 2 equivalents of epoxide for an amine ) in 10 mL of dimethylformamide DMF was placed in a 50 mL flask mounted on a reflux mount equipped with a condenser and magnetic bar, as well as a hot plate oil bath. The reaction mixture was stirred and heated to a temperature of 80 ° C. at the beginning of the reaction and then re-heated at 100 ° C. for 2 days until a brown two-phase mixture was obtained. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner. The solid phase was then dissolved in methanol, the latter being removed in a rotary evaporator.
    The product obtained (12-ANH) was dried under reduced pressure and a brown paste was obtained.
    Characterization of the 12-ANH liquid crystal • The 12-ANH product was characterized by DSC under argon and with a heating rate of 10 ° K / min. The results of the calorimetric analysis are shown in FIG.
    The DSC spectrum shows the phase transition at -38 ° C (corresponding to the melting temperature) and an endothermic peak at 193 ° C (corresponding to the clarification temperature). • The 12-ANH liquid crystal has been observed in MOP. The liquid crystal is placed between two hydrophilic glass plates (thickness of the deposit: 3-5 μm), slid inside a heating plate and under a controlled atmosphere (nitrogen), itself mounted between the polarizer and the microscope analyzer.
    The MOP image obtained after shearing under glass plates at 185 ° C shows the appearance of very small birefringent zones representative of the observation of mesomorphic phase defects. • A 12-ANH powder deposit was made on a glass support for DRX analysis.
    The X-ray diffractogram, shown in FIG. 2, shows that the 12-ANH liquid crystal exhibits a hexagonal lamellar phase by diffraction peaks in the ratios Î3,,, ff. The evaluation of the hygroscopy of the 12-ANH liquid crystal was carried out by conducting the study of the vapor phase water sorption / desorption isotherm in accordance with the method described hereinafter.
    The sorption balance was equipped with an electronic microbalance and a dew point analyzer. The liquid crystal 12-ANH was previously dried at 60 ° C in a vacuum oven. Then the 12-ANH liquid crystal was again dried in the balance at 60 ° C with a ramp of 5 ° C / min until reaching a balance of 0.0010% setting for 10 minutes. If these conditions are not satisfied, the liquid crystal has been dried up to a maximum of 600 minutes. The end condition used was 0.005% change in mass for a duration of 20 minutes. During the sorption / desorption cycle, the maximum waiting time to reach equilibrium was 1000 minutes.
    Figure 3 shows the water sorption / desorption isotherms at 25 ° C, showing that the 12-ANH liquid crystal is hydrophilic. • 12-ANH liquid crystal has also been characterized by S AXS, depending on its hydration rate.
    The rate of hydration of the samples was controlled from a controlled atmosphere. The 12-ANH liquid crystal is oven dried at 60 ° C for one week under vacuum to obtain a dry sample. The dry 12-ANH liquid crystal was then analyzed by S AXS and the relative humidity of the room was measured using a hygrometer. The sample was then allowed to equilibrate for 1, 3, and 6 hours. To obtain a hydrated sample in a 100% moisture atmosphere, it was placed in a cup to avoid direct contact with water. This same cup was placed in a hermetic system filled with water. A water-saturated system was then obtained where the sample could hydrate.
    A shift of the "ionomer peak" with the hydration of the 12-ANH liquid crystal is observed (FIG. 4).
    The "ionomeric peak" is the signature of the phase separation between hydrophilic and hydrophobic domains at the nanoscale. Its position (q) directly reflects the nanometric swelling state or the correlation distance between the hydrophilic (or hydrophobic) domains (d = 2π / q). The more this peak is shifted towards the smaller values of "q" (more d increases), the greater the amount of water in the product.
    Example 2 Preparation of a 12-ANLi Liquid Crystal According to the Invention
    This product was synthesized according to a protocol similar to that described in Example 1, using 1.050 g of ANLi (4.73 mmol) instead of ΓΑΝΗ with 1.741 g (9.46 mmol) of 1,2-epoxydodecane in mL of DMF. The reaction is maintained at 70 ° C for 3 days. A brown yellow powder (12-ANLi) is obtained.
    Characterization of the 12-ANLi liquid crystal • The results of DSC analysis under argon and with a heating rate of 10 ° K / min are shown in Figure 5. The DSC spectrum shows the phase transition at 6.25 ° C ( corresponding to the melting temperature) and an endothermic peak at 226 ° C (corresponding to the clarification temperature). A deposition of 12-ANLi powder was carried out on a glass support for X-ray diffraction analysis. The XRD analysis represented in FIG. 6 shows that the 12-ANLi compound exhibits a lamellar phase by diffraction peaks. in ratios 2, 3, 4, 5. • The evaluation of the hygroscopy of the 12-ANLi liquid crystal was carried out by conducting the study of the vapor phase sorption / desorption isotherm of water, according to the detailed protocol in example 1.
    Figure 7 shows the water sorption / desorption isotherms at 25 ° C, showing that the 12-ANLi liquid crystal is hydrophilic.
    Example 3 Preparation of the 6-ANH liquid crystal according to the invention
    3.101 g (13.47 mmol) of ANH and 3.35 mL (26.94 mmol) of 1,2-epoxyhexane in 15 mL of dimethylformamide DMF were placed in a 50 mL flask mounted on a reflux mount equipped with a condenser and a magnet bar, as well as an oil bath on a hot plate. The reaction mixture was stirred and heated under argon at 100 ° C for 120 h until a homogeneous brown mixture was obtained. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner.
    The product obtained (6-ANH) was dried under reduced pressure and a brown paste was obtained.
    Example 4 Preparation of the 6-ANLi liquid crystal according to the invention
    3.222 g (13.62 mmol) of ANLi and 3.39 mL (27.24 mmol) of 1,2-epoxyhexane in 15 mL of dimethylformamide DMF were placed in a 50 mL flask mounted on a reflux mount equipped with a condenser and a magnet bar, as well as an oil bath on a hot plate. The reaction mixture was stirred and heated under argon at a temperature of 100 ° C for 144 h until a homogeneous very dark red mixture was obtained. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner.
    The product obtained (6-ANLi) was dried under reduced pressure and a red wine-red paste was obtained.
    Temperature SAXS observations confirmed the existence of an organized structure, proving that 6-ANLi is a thermotropic ionic liquid crystal.
    Example 5 Preparation of the 8-ANLi liquid crystal according to the invention
    3.03 g (13.19 mmol) of ANLi and 4.21 mL (26.38 mmol) of 1,2-epoxyoctane in 15 mL of dimethylformamide DMF were placed in a 50 mL flask mounted on a reflux mount. equipped with a condenser and a magnet bar, as well as a hot plate oil bath. The reaction mixture was stirred and heated under argon at 60 ° C for 96 h, then at 65 ° C for 144 h, then at 75 ° C for 264 h and then at 85 ° C for 3 weeks until 'to obtain a homogeneous mixture very dark. The products of the reaction were precipitated in a large volume of diethyl ether and then fired on Buchner.
    The product obtained (8-ANLi) was dried under reduced pressure and a dark red powder was obtained.
    Example 6 Preparation of the 14-ANH liquid crystal according to the invention
    3.136 g (13.62 mmol) of ANH and 8.057 mL (27.25 mmol) of 1,2-epoxytetradecane in 15 mL of dimethylformamide DMF were placed in a 50 mL flask mounted on a reflux mount equipped with a refrigerant and a magnet bar, as well as an oil bath on a hot plate. The reaction mixture was stirred and heated under argon at 90 ° C for 144 h until a homogeneous very dark red mixture was obtained. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner.
    The product obtained (14-ANH) was dried under reduced pressure and an orange red powder was obtained.
    Example 7 Preparation of the 14-ANLi liquid crystal according to the invention
    3.008 g (13.12 mmol) of ANLi and 7.76 mL (26.25 mmol) of 1,2-epoxytetradecane in 15 mL of dimethylformamide DMF were placed in a 50 mL flask mounted on a reflux mount equipped with a condenser and a magnet bar, as well as an oil bath on a hot plate. The reaction mixture was stirred and heated under argon at 90 ° C for 144 h until a very dark brown homogeneous mixture was obtained. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner.
    The product obtained (14-ANLi) was dried under reduced pressure and a red powder was obtained.
    Observations by DSC, MOP and S AXS confirmed that 14-ANLi is a thermotropic ionic liquid crystal.
    The DSC spectrum does not show the phase transition corresponding to the melting temperature (because less than the minimum temperature of the measurement) but has three endothermic peaks characteristic of three mesomorphic phase changes. The evolution of the AXS spectra S up and down in temperature, as well as the MOP shots, made it possible to identify the three mesomorphous phases: lamellar, lamellar-columnar and columnar.
    Example 8 - Preparation of the 16-ANLi liquid crystal according to the invention
    2.991 g (13.12 mmol) of ANLi and 7.380 g (26.10 mmol) of 1,2-epoxyhexadecane in 25 mL of dimethylformamide DMF were placed in a 100 mL flask mounted on a reflux mount equipped with a refrigerant and a magnet bar, as well as an oil bath on a hot plate. The reaction mixture was stirred and heated under argon at 100 ° C for 2 weeks until a homogeneous, very dark brown mixture was obtained. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner.
    The product obtained (16-ANLi) was dried under reduced pressure and a red powder was obtained.
    The observations by DSC and S AXS confirmed that 16-ANLi is a thermotropic ionic liquid crystal with two main lamellar-type mesomorphic phases with a mesomorphic phase transition around 50 ° C.
    Example 9 Preparation of the 8F-ANH Liquid Crystal According to the Invention
    1.00 g of ANH (4.48 mmol) and 4.26 g (8.95 mmol) of 1,2-epoxy-1H, 1H, 2H, 3H, 3H-heptadecafluorodecane in 10 mL of DMF were placed. in a flask equipped with a condenser and a magnetic bar. The reaction mixture was stirred and heated at 80 ° C under air for 2 days until a homogeneous mixture was obtained. The compound was precipitated in diethyl ether and filtered on Buchner. The product was dried under reduced pressure, and a stable pinkish gel was obtained (8F-ANH).
    Example 10 Preparation of the BGE-ANLi liquid crystal according to the invention
    3.034 g (13.24 mmol) of ANLi and 3.99 mL (26.48 mmol) of butyl glycidyl ether were placed in a 25 mL flask mounted on a reflux mount equipped with a condenser and a magnetic bar. , as well as an oil bath on a hot plate. The reaction mixture was stirred and heated under argon at 70 ° C for 24 h, then at 80 ° C for 96 h, then at 90 ° C for one week until a very homogeneous mixture was obtained. dark. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner.
    The product obtained (BGE-ANLi) was dried under reduced pressure and a red powder was obtained.
    Example 11 - Preparation of the 12-AN'Li liquid crystal according to the invention
    2.903 g (12.67 mmol) of AN'Li and 6.15 mL (25.33 mmol) of 1,2-epoxydodecane in 15 mL of dimethylformamide DMF were placed in a 50 mL flask mounted on a reflux equipped with a condenser and a magnetic bar, as well as an oil bath on a hot plate. The reaction mixture was stirred and heated under argon at 100 ° C for 2 weeks until a homogeneous, very dark brown mixture was obtained. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner.
    The product obtained (12-AN'Li) was dried under reduced pressure and a red powder was obtained.
    The observations by DSC and SAXS confirmed that 12-AN'Li is a thermotropic ionic liquid crystal with an indefinite organization between 10 ° C and 70 ° C, then lamellar type beyond 70 ° C.
    Example 12 - Preparation of the 16-AN'Li liquid crystal according to the invention
    3.160 g (13.79 mmol) of AN'Li and 7.80 g (27.57 mmol) of 1,2-epoxyhexadecane in 25 mL of dimethylformamide DMF were placed in a 100 mL flask mounted on a reflux mount. equipped with a condenser and a magnet bar, as well as a hot plate oil bath. The reaction mixture was stirred and heated under argon at 90 ° C for 2 weeks until a very dark brown homogeneous mixture was obtained. The products of the reaction were precipitated in a large volume of diethyl ether and then filtered on Buchner.
    The product obtained (16-AN'Li) was dried under reduced pressure and a red powder was obtained.
    The observations by DSC and SAXS confirmed that 16-AN'Li is a thermotropic ionic liquid crystal having a columnar organization of ambient temperature at 80 ° C, then a lamellar phase up to 160 ° C (clarification temperature).
    Example 13 - Ion Conductivity Measurements
    Measurements were made between the upper and lower plane of a plane / plane rheometer using disposable geometries in an oven allowing conductivity measurements up to 250 ° C. The two parallel planes represent the two electrochemical impedance spectroscopy measurement electrodes and they have been connected to the working electrode and the counter electrodes of an impedance spectrometer.
    The product to be tested was placed on the lower geometry and the upper geometry descended to an applied force of 5 N. The system was heated until the product melted while maintaining a force of 5 N, so to ensure a perfect contact surface between the sample and the electrodes. As the temperature increased, the measurement gap decreased and the value (displayed digitally on the rheometer) was read in order to calculate the ionic conductivity. Impedance spectroscopy is performed with an amplitude of 10 mV from 1 MHz to 10 mHz for each temperature.
    The results obtained are shown in FIGS. 8 and 9 (ionic conductivity in S / cm as a function of 1000 / T, where T is the temperature in Kelvin).
    The thermotropic ionic liquid crystal molecules according to the invention 12-ANLi, 12-AN'Li, 14-ANLi, 16-ANLi and 16-AN'Li have an ionic conductivity over a wide temperature range, of about 10 S / cm at about 60 ° C to about 10 5 S / cm at about 200 ° C.
    These thermotropic ionic liquid crystal molecules according to the invention are suitable for use as electrolytes in an electrochemical system, in particular in a lithium battery.
    权利要求:
    Claims (22)
    [1" id="c-fr-0001]
    Thermotropic ionic liquid crystal molecule comprising: a so-called rigid part, consisting of a polycyclic group Ar formed from two to six rings of which at least one is aromatic, said rings comprising, independently of each other, from 4 to 6 linkages, said polycyclic group may include up to 18 heteroatoms, in particular selected from the group consisting of S, N and O; A part, said flexible, formed of one or more linear or branched, saturated or unsaturated, fluorinated or non-fluorinated aliphatic chains, the said chain or chains being optionally interrupted by one or more heteroatoms, by one or more metalloids and / or by one or more (hetero) rings, aromatic or otherwise, of 4 to 6 members, and optionally substituted with one or more groups selected from the group consisting of hydroxyl, -NH 2 and oxo; said flexible portion being covalently bonded, directly or via a spacer, to said rigid portion; and one or more ionic groups -AX "CX +, -Ax 'being an anionic group covalently bonded to said rigid portion, with x being equal to 1 or 2, -Ax' being selected from the group consisting of sulfonate anions, sulfonylimide of formula -SO2-N'-SO2CyF2y + i with y integer varying from 0 to 4, borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulphide, selenate, nitrate and perchlorate, and Cx + being a counter-cation anionic group -Ax ', selected from the group consisting of H * and cations of alkali and alkaline earth metals.
    [2" id="c-fr-0002]
    2. Molecule according to the preceding claim, wherein said polycyclic group Ar has one of the following skeletons:




    [3" id="c-fr-0003]
    3. Molecule according to claim 1 or 2, wherein said polycyclic group Ar is an aromatic bicyclic group, in particular having an aromatic skeleton naphthalene, and more particularly Ar is a naphthalene group.
    [4" id="c-fr-0004]
    4. A molecule according to any one of the preceding claims, wherein the flexible portion is formed of: - a single branched aliphatic chain, having a linear sequence of at least 6 covalent bonds; or - at least two linear or branched aliphatic chains, each of the chains having a linear sequence of at least 6 covalent bonds.
    [5" id="c-fr-0005]
    A molecule according to any one of the preceding claims, wherein each of the aliphatic chains is formed of a single segment or a linear sequence of at least two chain segments, in particular two or three chain segments. different chemical nature.
    [6" id="c-fr-0006]
    A molecule according to any one of the preceding claims, wherein said at least one aliphatic chain (s) forming said flexible portion is / are covalently bound directly to one or more carbon atoms or heteroatoms of the Ar group forming the rigid part.
    [7" id="c-fr-0007]
    7. A molecule according to any one of claims 1 to 5, wherein said one or more aliphatic chain (s) forming said flexible portion is / are covalently bonded via a spacer to one or more carbon atoms. carbon or heteroatoms of the Ar group forming the rigid part.
    [8" id="c-fr-0008]
    The molecule according to claim 7, wherein said one or more aliphatic chain (s) forming said flexible portion is / are covalently bound to a carbon atom of the Ar group via a higher valence atom or equal to 2, in particular via a nitrogen atom.
    [9" id="c-fr-0009]
    9. The molecule according to claim 7 or 8, wherein said flexible portion is formed of two linear alkyl chains, comprising from 4 to 18 carbon atoms, optionally substituted by one or more hydroxyl groups, optionally interspersed with one or more atoms of oxygen, said chains being bonded to a carbon atom of the Ar group via a nitrogen atom.
    [10" id="c-fr-0010]
    10. Molecule according to any one of the preceding claims, wherein said one or more anionic groups -Ax "are sulfonate anions or and anions of formula -SO2-N'-SO2-CyF2y + i with y varying from 0 to 4. and preferably 1, in particular sulphonate anions.
    [11" id="c-fr-0011]
    11. A molecule according to any one of the preceding claims, wherein Cx + is H * or the cation Li +.
    [12" id="c-fr-0012]
    12. Molecule according to any one of claims 1 to 5 or 7 to 11, characterized in that it has the following structure:

    (D) in which Ax 'and C ** are as defined according to any one of claims 1, 10 and 11, and Ej and E2 represent aliphatic chains, identical or different, as defined according to any one of the claims 1 and 4 to 9.
    [13" id="c-fr-0013]
    13. Molecule according to the preceding claim, wherein the chains Ej and E2 represent linear chains, identical or different, comprising from 6 to 16 carbon atoms, each being substituted by a hydroxyl group, optionally fluorinated, and optionally interspersed with a oxygen atom
    [14" id="c-fr-0014]
    14. Use of thermotropic ionic liquid crystal molecules as defined in any one of claims 1 to 13, in a mesomorphous state, as an electrolyte in an electrochemical system.
    [15" id="c-fr-0015]
    15. Use according to the preceding claim, wherein Cx + represents a Li + cation, as an electrolyte in a lithium battery.
    [16" id="c-fr-0016]
    16. Use according to claim 14, wherein Cx + is H *, as an electrolyte in a proton exchange membrane fuel cell, or a low temperature electrolyser.
    [17" id="c-fr-0017]
    An electrolyte comprising, if not being formed, thenmotropic ionic liquid crystal molecules as defined in any one of claims 1 to 13, in a mesomorphic state.
    [18" id="c-fr-0018]
    18. Electrolyte according to the preceding claim, characterized in that it has a viscosity greater than or equal to 10 mPa.s at a temperature between -60 ° C and 300 ° C.
    [19" id="c-fr-0019]
    19. An electrolyte according to claim 17 or 18, characterized in that it has an ionic conductivity at 20 ° C greater than or equal to 10 -9 S / cm, in particular between 10 -7 S / cm and 10 -5 S / cm and an ionic conductivity at 200 ° C greater than or equal to 10 -5 S / cm.
    [20" id="c-fr-0020]
    20. An electrochemical system comprising an electrolyte as defined in any one of claims 17 to 19, said electrolyte preferably being impregnated on a porous separator.
    [21" id="c-fr-0021]
    21. System according to the preceding claim, characterized in that it is a battery, in particular a lithium battery.
    [22" id="c-fr-0022]
    22. Porous separator characterized in that it is impregnated with an electrolyte as defined in any one of claims 17 to 19.
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    同族专利:
    公开号 | 公开日
    US10833368B2|2020-11-10|
    WO2017050769A1|2017-03-30|
    US20180261886A1|2018-09-13|
    FR3041358B1|2017-11-24|
    EP3353262A1|2018-08-01|
    EP3353262B1|2020-03-25|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1558864A|FR3041358B1|2015-09-21|2015-09-21|ELECTROLYTE FOR ELECTROCHEMICAL GENERATOR|FR1558864A| FR3041358B1|2015-09-21|2015-09-21|ELECTROLYTE FOR ELECTROCHEMICAL GENERATOR|
    US15/761,257| US10833368B2|2015-09-21|2016-09-20|Electrolyte for electrochemical generator|
    EP16767295.5A| EP3353262B1|2015-09-21|2016-09-20|Electrolyte for electrochemical generator|
    PCT/EP2016/072312| WO2017050769A1|2015-09-21|2016-09-20|Electrolyte for electrochemical generator|
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