EP3353231A1

EP3353231A1 - Solid electrolyte for an electrochemical generator

Info

Publication number: EP3353231A1
Application number: EP16766581.9A
Authority: EP
Inventors: Mélody LECLERE; Lionel Picard
Original assignee: Commissariat a lEnergie Atomique CEA; Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Current assignee: Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date: 2015-09-21
Filing date: 2016-09-19
Publication date: 2018-08-01
Also published as: US20180265634A1; FR3041350A1; US10870730B2; FR3041350B1; WO2017050691A1

Abstract

The invention relates to a compound comprising at least one entity of formula (I) in which G incorporates a polycyclic group Ar to which at least one anion A^x-is covalently bonded. The invention also relates to the use of at least one compound of formula (I), in the organised state, as a solid electrolyte in an electrochemical system.

Description

SOLID ELECTROLYTE FOR ELECTROCHEMICAL GENERATOR

The present invention relates to novel compounds that can be used as solid electrolytes.

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 Li ⁺ as an ionic species of current transport. In the case of a lithium battery for example, the Li ⁺ ion extracted from the cathode during the discharge of the battery is deposited on the anode, and conversely, it is extracted from the anode for s' intercalate in the cathode during charging.

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 electrolyte formulation 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 and ₄ N-BF ₄ ) 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 unfortunately pose safety and cost problems in the context of the implementation 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 matrix 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 salt or alkaline-earth (according to the chemistry of the electrodes). However, these electrolytes have limited ionic conductivity performance related to the cation transport mechanism, called "assisted" ([1]), and require a high temperature of use (60 to 80 ° C). The polymers are thus conductive in a gelled physical state, at the limit of the liquid.

As electrolyte polymer, the electrolytic membrane of the electrochemical generator systems of the fuel cell type can also be mentioned. membrane proton exchange, conventionally consisting of a polymer main chain and carbofluorée carrier pendant groups containing sulfonic acid functional groups, 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 application WO 00/05774 describes phase microseparation block copolymers consisting of a first ion conductive block, for example polyethylene oxide, and a second block, non-conductive and immiscible with the first block to ensure a micro-phase separation, for example of the 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 a mixture of a polystyrene bearing sulfonyl (trifluoromethylsulfonyl) imide and POE groups to produce an electrolyte membrane (Meziane et al., Electrochimica Acta, 2011, 57, 14-19). Unfortunately, these polymer electrolytes have insufficient ionic conductivities, of the order of 9.5 × 10 ^-3 mS / cm at 70 ° C. In addition, it is not possible for most current application areas to 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 ^-2 mS / cm, is obtained at 60 ° C. with a polymer comprising 78% by weight of POE.

There remains therefore a need for a solid electrolyte having both high ionic conductivity and good mechanical strength. The present invention aims precisely to propose new solid electrolytes, cationic or protonic conductors, having improved ionic conductivity and electrochemical stability.

More particularly, it relates, according to a first aspect, to a compound comprising at least one entity of formula (I):

in which :

A ^{x ~} is an anion of valence x equal to 1 or 2, selected from sulfonate anions, sulfonylimide of type -S0 ₂ -N ^~ -SO ₂ C _y F _{2y +} i with y an integer between 0 and 4; borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulphide, selenate, nitrate and perchlorate;

C ^{x +} is a counter-cation of the anion A ^{x ~} , chosen from the proton H ⁺ and the cations of the alkaline and alkaline-earth metals;

p is an integer ranging from 1 to 10, preferentially from 1 to 4;

E is an organic spacer comprising a linear sequence of at least two covalent bonds, in particular at least three covalent bonds and more particularly at least four covalent bonds;

n is an integer greater than or equal to 2, in particular ranging from 2 to 1800; and

G represents:

(a) a group , in which :

⁰ X is N, P or Si-R, with R representing a hydrogen atom or a Ci_4 alkyl group,

⁰ Ar is a cyclic poly group possessing 2 to 6 cycles of which at least one is aromatic, each ring comprising, independently of each other, 4 to 6-membered ring, said polycyclic group with up to 18 heteroatoms, in particular selected from S, N and O;

⁰ - □ represents a bond with Γ spacer E; and ⁰ - * represents one or more bonds with said anion (s) A ^{x ~} ;

*

□ - X-A

(b) a group 1 r-X ^ -! not

, in which :

⁰ Xi and X _2, identical or different, represent NR, O or S, with R representing a hydrogen atom or a Ci_4 alkyl group; in particular, X ₁ and X ₂ are both NH or O;

⁰ - □ represents a bond with spacer E; and

⁰ - * represents one or more bonds with said anion (s) A ^{x ~} ;

0 Ar is as defined previously;

the said anion (s) A ^{x ~} being covalently bound to the polycyclic group Ar.

As illustrated in the examples which follow, the inventors have shown that these compounds are proton or cationic conductors in their organized state.

By "organized state" is meant an organization, in the solid state, of the compound according to the invention. This organized state can still be described as frozen state or reduced mobility of the molecules between them. Without wishing to be bound by the theory, the polycyclic groups of the compounds according to the invention are organized with respect to one another to form "lamellae" spaced apart by the spacer chains.

This organized state may be further characterized by X-ray or neutron spectroscopy, where Bragg peaks and / or wide peaks are observable in a wave vector range of from 10 ^-4 to 6 A- ¹ . The width of these peaks depends on the size of the crystallites and the range of the correlations, the gradients of mesh parameters, ignoring the instrumental resolution of the apparatus.

Different states of organization are possible depending on the temperature of use. The organized state still corresponds to the state of the thermodynamically stable compound at a given temperature below its melting or decomposition temperature.

According to a particular embodiment, the organized state may be a crystalline state of the compounds according to the invention.

As detailed in the rest of the text, this state of organization can be obtained according to conventional techniques by "solvent" (for example, by controlled evaporation of the solvent) or by "melted" (for example, by extrusion). Thus, according to another of its aspects, the invention relates to the use of a compound comprising at least one entity of formula (I) as defined previously, in the organized state, as solid electrolyte in a electrochemical system.

It also relates to a solid electrolyte comprising, if not formed, one or more compounds comprising at least one entity of formula (I) as defined above, in the organized state.

By "solid electrolyte" is meant an electrolyte excluding the presence of a component in liquid form, and acting as both separator and ionic conductor in an electrochemical system.

The compounds according to the invention can be used as solid electrolytes in many electrochemical systems, such as generators, for example lithium batteries, electrochemical conversion systems, for example proton exchange membrane fuel cells ( PEMFC).

The use of the compounds according to the invention as solid electrolytes proves to be advantageous for several reasons.

Firstly, since these compounds are conductive in a solid state, in particular a crystalline state, they have a temperature of use as a strongly enlarged solid electrolyte.

An electrochemical system, for example a lithium battery, made from a solid electrolyte according to the invention can thus operate over a wide temperature range, preferably between -40 ° C. and 200 ° C., and more preferably between - 20 ° C and 200 ° C.

Moreover, the ionic conductivity of a solid electrolyte according to the invention is based on a "direct" conduction mechanism, by "jump"("hopping" in English) of the C ^{x +} cations of a polycyclic group Ar other, and not on an assisted mechanism as is the case for example polymer electrolytes proposed by Cohen et al. Molecular Transport in Liquids and Glasses, J. Chem. Phys. 31, 1164 (1959).

A solid electrolyte according to the invention thus leads to improved performances in terms of ionic conductivity.

On the other hand, as mentioned above, in addition to ensuring the passage of the ions from one electrode to the other, the solid electrolyte according to the invention also serves as separator, for electronically isolating the two electrodes of the electrochemical system.

Finally, as detailed in the rest of the text, the solid electrolyte according to the invention can also be incorporated into the composition of a composite electrode for an electrochemical system, for example the positive electrode of a lithium battery.

Other characteristics, variants and advantages of the solid compounds and electrolytes according to the invention, of their preparation and their implementation will emerge more clearly on reading the description, examples and figures which will follow, given for illustrative purposes and not limiting 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".

COMPOUNDS OF THE INVENTION

As mentioned above, the compounds according to the invention comprise at least one entity of formula (I) below:

in which :

A ^{~ x} is an anion of valency x equal to 1 or 2 selected from the sulfonate anion, sulfonylimide type -S0 ₂ -N ^~ -S0 ₂ CyF ₂ y ₊ iy being an integer between 0 and 4 (for example equal at 1); borate, borane, phosphate, phosphinate, phosphonate, silicate, carbonate, sulphide, selenate, nitrate and perchlorate;

C ^{x +} is a counter-cation of the anion A ^{x ~} , chosen from the proton H ⁺ and the cations of the alkaline and alkaline-earth metals, in particular the Li ⁺ cation;

p is an integer ranging from 1 to 10, preferably from 1 to 4 and in particular equal to 1; E is an organic spacer comprising a linear sequence of at least two covalent bonds, in particular at least three covalent bonds and more particularly at least four covalent bonds;

G represents:

*

Ar

(a) a group ^DD , in which:

⁰ Ar is polycychque group possessing 2 to 6 cycles of which at least one is aromatic, each ring comprising, independently of each other, 4 to 6-membered ring, said polycychque group with up to 18 heteroatoms, in particular selected from S, N and O;

⁰ - □ represents a bond with Γ spacer E; and

⁰ - * represents one or more bonds with said anion (s) A ^{x ~} ;

*

^□ - X- Ar-X ^ - □

or (b) a group, wherein:

⁰ - □ represents a bond with Γ spacer E; and

⁰ - * represents one or more bonds with said anion (s) A ^{x ~} ;

⁰ Ar is as defined previously;

the said anion (s) A ^{x ~} being covalently bonded to the polycychic group Ar.

In the context of the invention, the following terms mean:

"C _t -z" where t and z are integers, a carbon chain may have from t to z carbon atoms; for example C _1-4 a carbon chain which may have from 1 to 4 carbon atoms; "Alkyl", a saturated, linear or branched aliphatic group; for example a C 1-4 alkyl group represents a carbon chain of 1 to 4 carbon atoms, linear or branched, more particularly methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl;

- "(hetero) aromatic ring or not 4- to 6-membered ring", an unsaturated cyclic group, partially saturated or saturated, with 4, 5 or 6 members, optionally comprising one or more heteroatoms, in particular selected from oxygen, sulfur and nitrogen. An aromatic ring may especially be benzene;

- "polycyclic group" means a group having two or more aromatic (fused) rings fused (ortho-fused or ortho- and peri-condensed) to each other, that is, presenting, in pairs, at the minus 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 "polyhetero cyclic grouping".

"Alkali metals", the chemical elements of the first column of the periodic table of the elements, and more particularly chosen from 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 among beryllium, magnesium, calcium, strontium, barium and radium. Preferably, the alkaline earth metal is magnesium or potassium.

In the definition of the organic spacer E, it is understood that the expression "linear sequence" is opposed to a so-called "cyclic" sequence (for example in a benzene structure). E thus comprises a linear (non-cyclic) chain of at least two covalent bonds, for example two carbon-carbon bonds, in particular at least three covalent bonds.

Preferably, n in formula (I) above may be between 2 and 1500, in particular between 2 and 300.

According to a particular embodiment, the compound of the invention may be a (co) polymer comprising at least one entity of formula (I) defined above. In particular, a copolymer according to the invention may have different entities of formula (I). It may be for example a block copolymer, the blocks being differentiated by the nature of the group G, the spacer E and / or the anion A ^{x ~} .

According to a particularly preferred embodiment, the compounds according to the invention are polymers comprising, or even being formed, monomeric units of formula (F) below:

in which G, E, A ^{x ~} , C ^{x +} and p are as defined above.

In particular, the monomeric units of formula (F) may represent represent more than 60%, in particular more than 80% and more particularly more than 90%, of the total weight of the monomeric units forming the polymer.

According to a particular embodiment, a polymer according to the invention is formed solely of monomeric units of formula (F). It may more particularly have a degree of polymerization (n) of between 2 and 1,500, in particular between 2 and 300.

According to a first variant embodiment, the polycyclic groups, Ar, are side groups of the main chain of the compound according to the invention.

In other words, the group G in the formula (I) according to the invention represents

Ar a group ^DD , in which:

⁰ X is N, P or Si-R, with R representing a hydrogen atom or a Ci_4 alkyl group; preferably X is N;

⁰ Ar is a polycyclic group possessing 2 to 6 cycles of which at least one is aromatic, each ring comprising, independently of each other, 4 to 6-membered ring, said polycyclic group with up to 18 heteroatoms, in particular selected from S, N and O;

⁰ - □ represents a bond with spacer E; and

⁰ - * represents one or more bonds with said anion (s) A ^{x ~} ; the said anion (s) A ^{x ~} being covalently bound to the polycyclic group Ar.

In particular, according to a particularly preferred embodiment, the compounds according to the invention are polymers comprising, if not being formed, monomeric units of formula (II) below:

C ^{x +}

Ar

wherein E, Ar, A ^{x ~} , C ^{x +} and p are as previously defined or described more precisely below.

According to a second variant embodiment, the polycyclic groups, Ar, are integrated in the main chain of the compound according to the invention.

^□ - X- Ar-X ^ - □

a group, in which:

⁰ Xi and X _2, identical or different, represent NR, O or S, with R representing a hydrogen atom or a Ci_4 alkyl group; especially Xi and X ₂ both represent NH or O;

⁰ - □ represents a bond with spacer E; and

⁰ - * represents one or more bonds with said anion (s) A ^{x ~} ;

the said anion (s) A ^{x ~} being covalently bound to the polycyclic group Ar.

Preferably, Ar is a polycyclic group comprising from 2 to 4 rings, with in particular at least one of the rings being aromatic. According to a variant, Ar is an aromatic polycyclic group formed from 2 to 6 aromatic rings.

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 several carbon atoms are replaced by one or more heteroatoms, in particular chosen from 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.

Thus, according to a particularly preferred embodiment, the compounds according to the invention are polymers comprising, or even being formed, monomeric units of formula (III) below:

wherein E, A ^{x ~} and C ^{x +} are as defined above or detailed hereinafter.

As indicated above, E in formula (I) above (in particular, in formula (Γ), (II) or (III) above) represents an organic spacer having a linear sequence of at least two covalent bonds, in particular at least three covalent bonds, and more particularly at least four covalent bonds.

Advantageously, this spacer makes it possible to ensure, during the implementation of the compound according to the invention to form a solid electrolyte, the arrangement of the polycyclic groups Ar with respect to one another to reach an organized proton conductive state or cationic.

This organic spacer can be of various natures.

Preferably, the organic spacer E is a linear or branched aliphatic chain, saturated or unsaturated, with at least two covalent bonds, said chain being optionally interrupted by one or more heteroatoms (s), in particular S, O or N, by one or more metalloids, for example silicon, and / or one or more (hetero) rings, aromatic or otherwise, of 4 to 6 members; said chain being optionally substituted by one or more fluorine atoms and / or by one or more R 1 groups, R 1 represents a group chosen from a hydroxyl group, optionally in protonated form -O ^" C ⁺ , an -NH ₂ group and an oxo group.

In particular, R 1 is a hydroxyl group, optionally in protonated form -O ^" C ⁺ .

As illustrated in the examples which follow, the substituent groups of the aliphatic chain, R 1, can in particular result from nucleophilic addition or substitution reactions used for the synthesis of the compound according to the invention.

The implementation of a fluorinated chain advantageously makes it possible to confer on the spacer a great flexibility and thus to obtain states of organization of the compound according to the invention even at very low temperature (between -80 ° C. and -60 ° C. ° C for example). Moreover, fluorine has a very good electrochemical stability.

Preferably, the organic spacer E may represent a saturated linear aliphatic chain C ₄ to C ₂ o, said chain being optionally interrupted by one or more heteroatoms, in particular one or more oxygen atoms, and / or by one or more a plurality of aromatic or non-aromatic rings of 4 to 6 members, in particular one or more benzene rings, said chain being optionally substituted with one or more hydroxyl groups, preferably in protonated form -O ^" C ⁺ .

Advantageously, the hydroxyl functions of the organic spacer E of the compound according to the invention are protonated (-O ^" C ⁺ ), prior to its implementation as solid electrolyte, as detailed in the rest of the text, so that the Hydroxyl pendant functions do not immobilize C ⁺ cations during the operation of the electrochemical system, which could be detrimental to the ionic conductivity of the solid electrolyte Thus, C ⁺ cations immobilized at the spacer do not participate in the charge transfer.

In the formula (I) (in particular the formula (Γ), (II) or (III)) above, the anion A ^{x ~} may be more particularly selected from sulfonate anions (SO3) and trifluoromethylsulfonylimide (TFSI).

Preferably, A ^{x ~} is a sulfonate anion. According to an alternative embodiment of the invention, C ^x represents the proton H. As detailed in the rest of the text, such compounds can be advantageously used as solid electrolyte in a lithium battery.

According to another variant embodiment of the invention, C ^{x +} represents the Li ⁺ cation. As detailed in the rest of the text, such compounds can be advantageously used as solid electrolyte in a proton exchange membrane fuel cell (PEMFC) or a low temperature electrolyser.

It is understood that the definitions given above for G, E, n, A ^{x ~} and C ^{x +} can be combined, as far as possible, to define other particular embodiments.

Thus, by way of example of compounds in accordance with the invention, may be more particularly mentioned polymers comprising, in particular constituted, monomeric units of formula (IV) below:

in which E and C ^x are as defined according to one of the definitions presented above. Preparation of the compounds of the invention

The compounds according to the invention can be prepared by implementing nucleophilic substitution or addition methods known to those skilled in the art, as detailed below.

According to a first variant embodiment, the compounds of the invention, for

*

Wherein G represents (a) a ^DD group may be prepared by a process comprising at least the bringing together of a compound having the following structure (ai)

C ^{x +}

(A ^{x "} -j- Ar- Nu

(have)

where Nu represents a difunctional nucleophilic function, in particular an -NH ₂ , -PH ₂ or -SiRH _{2 function} with R representing a hydrogen atom or a C 1-4 alkyl group,

with a precursor of the spacer E, having two identical electrophilic functions, in particular chosen from epoxide, halogen, isocyanate, nitrile, thiocarbonyl and carbonyl functions, under conditions conducive to their interaction according to a substitution or addition reaction nucleophile.

By way of example, the polymers according to the invention having monomeric units of formula (II) above can be obtained via a nucleophilic addition reaction between a compound of formula

C ^{x +}

(A ^{x "} -Ar-NH ₂

'P

and a precursor of the spacer E, having two identical electrophilic functions, for example epoxide functional groups.

This first variant of preparation of compounds according to the invention is illustrated in the examples which follow.

Alternatively, it is also possible to perform the substitution or nucleophilic addition reaction between a compound comprising the polycyclic group carrying a difunctional electrophilic function, for example of the anhydride type, and a precursor of the spacer E with two mono-functional nucleophilic functions.

Similarly, with regard to the compounds of the invention for which G

*

^□ - X- Ar-X ^ - □

represents (b) a group, they can be prepared, according to an alternative embodiment, according to a process comprising at least one step of bringing into contact a compound having the following structure (b):

where Nu ', identical or different, represent mono-functional nucleophilic functions, in particular chosen from hydroxyl, thiol or secondary amine functions,

Alternatively, it is also possible to perform the substitution or nucleophilic addition reaction between a compound comprising the (poly) cyclic group carrying two electrophilic functions and a precursor of the spacer E having two mono functional nucleophilic functions, identical or different, in particular chosen from hydroxyl, thiol and secondary amine functions.

Of course, it is for the skilled person to adjust the synthesis conditions to obtain the compounds according to the invention.

USE AS SOLID ELECTROLYTE

The compounds according to the invention can advantageously be used, in their organized state, as solid electrolytes, in particular in an electrochemical system, in particular in a lithium battery.

Preparation of the solid electrolyte according to the invention

As mentioned above, the compounds of formula (I) according to the invention are protonic or cationic conductors in their organized state.

The organized state is more particularly a solid state. It may be in particular a crystalline state.

The solid electrolyte formed according to the invention can be in any suitable form, for example in the form of a sheet, a film or a membrane.

The solid electrolyte according to the invention has good properties of ionic conductivity. According to one embodiment, the solid electrolyte according to the invention has an ionic conductivity at 120 ° C. of greater than or equal to 10 ^{~ 9} S / cm, in particular between 10 ^{~ 8} and ⁵ × 10 ⁵ S / cm, in particular between 10 ^{~ 8} and 10 ^{~ 5} S / cm.

Preferably, the solid electrolyte according to the invention has an ionic conductivity at 200 ° C greater than or equal to 10 ^{~ 7} S / cm, in particular between 10 ^{~ 7} and 10 ^"3 S / cm.

The solid electrolyte according to the invention, comprising one or more compounds of the invention described above, in an organized state, can be prepared according to known techniques, by "solvent" (for example, by controlled evaporation of the solvent) or by "melted" (for example, by extrusion).

Of course, one skilled in the art is able to adjust the method of preparation of the solid electrolyte with regard to the electrochemical system in which it is intended to be implemented.

Thus, according to a first variant embodiment, the solid electrolyte according to the invention can be obtained by controlled evaporation.

More specifically, a film (or layer) comprising at least one solid electrolyte according to the invention may be prepared on the surface of a substrate, according to a process comprising at least the steps consisting in:

(a1) providing a solution comprising at least one compound according to the invention in a polar solvent;

(b1) depositing said solution of step (a1) at the surface of said substrate; and

(cl) evaporating the solvent under conditions conducive to the formation of a film comprising at least one solid electrolyte formed of said compound of formula (I) in its organized state.

The polar solvent in step (a1) may for example be the

Ν, Ν-dimethylformamide (DMF), dimethylacetamide (DMAc), monoalcohols including methanol, water.

Those skilled in the art are able to adjust the evaporation conditions of the solvent to obtain the desired organized state.

One or more subsequent exposure steps of the film, formed after evaporation of the solvent, to an electric field, magnetic field or ionizing radiation, in particular photonic, can be operated, so as to promote the desired organized state.

Preferably, the substrate on the surface of which is formed the film comprising the solid electrolyte according to the invention has the least possible surface defects, to allow obtaining an optimal organized state, for example having good crystallinity , the compound according to the invention ensuring optimum ionic conductivity.

According to yet another alternative embodiment, a solid electrolyte film according to the invention, supported by a substrate or self-supporting, can be obtained by molten route, in particular by extrusion.

Melt extrusion techniques are known to those skilled in the art.

More specifically, the method for preparing a solid electrolyte film can implement at least the steps consisting in:

(a2) having a powder formed of at least one compound according to the invention;

(b2) melt extruding said powder in the form of a solid electrolyte film formed of said compound of formula (I) in its organized state; and

(c2) spreading said electrolyte film, optionally on the surface of a substrate.

As before, one or more subsequent stages of exposure of the film to an electric field, magnetic field or to ionizing radiation, in particular photonic radiation, may be operated, so as to favor obtaining the desired organized state.

The film comprising the solid electrolyte may have a thickness of between 5 and 50 μιη, in particular about 5 μιη.

Electrochemical system

The solid 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 a solid electrolyte according to the invention.

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, lithium-sulfur accumulator.

According to a particular embodiment, the solid electrolyte is implemented in a battery, in particular a lithium battery.

Separator electrolyte

An electrochemical system according to the invention generally comprises at least one positive electrode and one negative electrode, between which there is a solid electrolyte film acting as both an ionic conductor and a separator between the positive and negative electrodes.

In the remainder of the text, the solid electrolyte layer according to the invention, intended to act as a separator between the positive and negative electrodes of an electrochemical system, will be more simply referred to as the "separating electrolyte".

The separating electrolyte may be formed, according to one of the methods described above, on the surface of a substrate consisting, at least in part, of an electrode of the electrochemical system.

The substrate may for example be formed of a multilayer stack comprising at least one current collector and an electrode suitable for producing the electrochemical system, for example a composite electrode as described below, on the surface of which is formed separating electrolyte.

The separating electrolyte according to the invention may have a thickness of between 5 and 50 μιη, in particular of approximately 5 μιη.

The elaboration of the desired electrochemical system integrating the separating electrolyte according to the invention is within the competence of those skilled in the art. Those skilled in the art are thus able to implement conventional techniques, in particular for the formation of a second solid layer intended to be used as an electrode, on the surface of the solid electrolyte layer formed as described previously.

For example, a lithium battery can be formed, conventionally, by two electrodes, namely a positive electrode and a negative electrode. The positive electrode generally comprises, as electrochemically active material, lamellar compounds such as LiCoO ₂ , LiNiO ₂ and mixed Li (Ni, Co, Mn, Al) O ₂ , or spinel structure compounds of compositions close to LiMn. ₂ 0 _4, phosphates of lithium, particularly LiFeP0 _4.

The negative electrode generally comprises, as an electrochemically active material, lithium metal in the case of primary accumulators, or intercalation materials such as graphite carbon, or lithium titanium oxide (Li ₄ Ti ₅ 0i ₂ ) in the case of accumulators based on lithium-ion technology.

current collectors, generally of copper for the negative electrode, or of aluminum for the positive electrode, which allow the circulation of the electrons, and therefore the electronic conduction, in the external circuit; and

the separating electrolyte according to the invention, in which ionic conduction occurs which ensures the passage of lithium ions from one electrode to the other, and which also acts as a separator, making it possible to prevent contact between the positive electrodes; and negative.

It may be in particular a lithium metal battery, comprising a lithium metal anode and a cathode comprising at least one positive electrode active material, between which there is a solid electrolyte according to the invention. Composite electrode

At least one of the electrodes of the electrochemical system according to the invention, for example the positive electrode of a lithium battery, may further comprise a solid electrolyte according to the invention.

Such a composite electrode makes it possible to optimize the solid electrolyte / electrode interface of the electrochemical system, insofar as the electrolyte of the invention can not penetrate the porous material of the electrode. Moreover, the use of a solid electrolyte according to the invention in the composition of the cathode makes it possible in particular to prevent the formation of a concentration gradient in the thickness of the cathode during cycling, and thus of to improve the power performance of the battery, or to increase the grammage of the cathode (i.e., the amount of positive electrode active material / cm ² / face. Thus, according to yet another of its aspects, the present invention relates to a composite electrode comprising at least one solid electrolyte according to the invention.

It also relates to an electrochemical system comprising at least one such composite electrode.

In the particular case of a lithium metal battery, only the cathode can be a composite electrode.

In other battery cases, both the positive electrode and the negative electrode are preferably composite electrodes.

A composite electrode according to the invention may be more particularly formed of a composite material comprising, in addition to the solid electrolyte according to the invention, one or more active substances, one or more conductive additives and optionally one or more binders.

The solid electrolyte of a composite electrode according to the invention can be obtained by a "solvent route" technique.

By way of example, a composite electrode that can be used for example as a positive electrode in a lithium battery can be formed via the following steps:

(a) preparing a dispersion comprising, in one or more solvents, one or more compounds of the invention; one or more active substances, one or more conductive additives and optionally one or more binders.

As mentioned above, the active materials for a positive composite electrode may be chosen from lithium intercalation materials such as lamellar oxides of lithium transition metals, olivines (LiFePO ₄ ), LiMn ₂ O ₄ , or spinels ( for example spinel LiNi0 5Mni _i5 0 ₄ ).

The electronic conductive additives may be chosen for example from carbon fibers, carbon black, carbon nanotubes and their analogues.

The binders may be chosen from fluorinated binders, for example polytetrafluoroethylene, polyvinylidene fluoride (PVDF), polysaccharides or latices, in particular styrene-butadiene rubber (SBR or styrene-butadiene rubber).

The dispersion, more commonly called "ink", can be homogenized before spreading, for example using a deflocculator at a speed between 2 and 5000 rpm with a deflocculated disk geometry. The value of the shear gradient can vary between 10 and 2000 s ^-1 .

(b) spreading the dispersion thus prepared on the surface of a current collector, for example of the aluminum, copper, nickel or iron type; and

(c) evaporating said solvent (s) to form the electrode film.

The evaporation can be carried out by drying, for example in an oven, at a temperature between 50 ° C and 120 ° C, in particular about 80 ° C, for a period of between 1 hour and 24 hours.

The composite electrode may more particularly comprise from 30 to 60% by weight of solid electrolyte according to the invention, in particular about 40% by weight of solid electrolyte, relative to the total weight of the electrode.

The remainder of the composite electrode may be more particularly formed from 80 to 95% of active material (s) and 0 to 1% of additive (s) conductor (s).

The composite electrode according to the invention may have a thickness of between 20 μιη and 400 μιη, in particular between 100 μιη and 250 μιη.

The invention further relates, in another of its aspects, to an electrochemical system comprising:

a solid electrolyte film (separating electrolyte) as described above, serving as both an ionic conductor and a separator between the positive and negative electrodes, and

at least one composite electrode (the positive electrode and / or the negative electrode) 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.

FIGURES

Figure 1: Infrared spectrum of the polymer PI according to the invention formed according to Example 1;

FIG. 2: Infrared spectrum of the lithiated PI polymer according to the invention formed according to Example 2; FIG. 3: ATG thermogravimetric analysis diagram obtained for the lithiated P1 polymer powder formed according to Example 2;

FIG. 4: Plate obtained by polarized optical microscope of the organically-lithiated (crystalline) P1 polymer prepared according to Example 2 on a silicon substrate;

FIG. 5: XRD diagram obtained for the lithiated PI polymer in the organized state

(crystalline) prepared according to Example 2;

Figure 6: Schematic representation of the TLM structure and the characteristic of the total resistance as a function of the distance between the contacts;

Figure 7: Infrared spectrum of the polymer P2 according to the invention formed according to Example 4;

FIG. 8: ATG thermogravimetric analysis diagram obtained for the polymer powder P2 formed according to Example 4;

FIG. 9: Infrared spectrum of the lithiated P2 polymer according to the invention formed according to Example 5;

FIG. 10 is a photograph obtained by polarized optical microscope of the crystallized P2 polymer in the (crystalline) organized state, prepared according to example 5 on a copper substrate;

11: DRX diagram obtained for the crystalline P2 polymer in the organized (crystalline) state, prepared according to Example 5;

12: Infrared spectrum of the polymer P3 according to the invention formed according to Example 6;

FIG. 13: ATG thermogravimetric analysis diagram obtained for the polymer P3 powder formed according to Example 6;

14: Infrared spectrum of the polymer P6 according to the invention formed according to Example 10.

15: Infrared spectrum of the polymer P7 according to the invention formed according to Example 11.

FIG. 16: ATG thermogravimetric analysis diagram obtained for the P7 polymer powder formed according to Example 11;

17: Infrared spectrum of the polymer P8 according to the invention formed according to Example 12;

FIG. 18: ATG thermogravimetric analysis diagram obtained for the P8 polymer powder formed according to Example 12; Figure 19: Conductivity of the polymer P2 obtained as a function of the temperature formed according to Example 4;

Figure 20: Infrared spectrum of Pro-ANTFSA according to the invention formed according to Example 13-Step 3.

Figure 21: Monitoring of the evolution of the pH according to the molar quantity of

L1OH.H ₂ O of Example 13-Step 4.

FIG. 22: Infrared spectrum of the polymer P9 according to the invention formed according to Example 15.

FIG. 23: ATG thermogravimetric analysis diagram obtained for the P9 polymer powder formed according to Example 15;

FIG. 24: Infrared spectrum of the polymer P10 according to the invention formed according to Example 16.

FIG. 25: ATG thermogravimetric analysis diagram obtained for the P10 polymer powder formed according to Example 16;

FIG. 26: Infrared spectrum of the polymer P 1 according to the invention formed according to Example 17.

FIG. 27: ATG thermogravimetric analysis diagram obtained for the polymer powder P 1 formed according to Example 17;

Figure 28: Ionic conductivity of the polymers P2, P7, P9, P 10 and PI 1 obtained as a function of the temperature under the planes of a rheometer.

EXAMPLES EXAMPLE 1

Preparation of a PI polymer according to the invention from lithium 4-amino-l-naphthalenesulphonate and butadiene diepoxide

Synthesis of lithium 4-amino-1-naphthalenesulphonate (ANLi) 1.340 g of 4-amino-1-naphthalenesulfonic acid (ANH) and 0.210 g of lithium hydroxide monohydrate (LiOH, H ₂ O) are added in 20 ml of distilled water. The reaction medium is stirred for 1 night at room temperature. The excess of ANH is removed by filtration. The filtrate is then concentrated by evaporation of the solvent under reduced pressure. After two washings with ethanol, a pink powder is obtained. Monocrystals were obtained by crystallization in water.

X-ray diffraction analysis (XRD) shows that the ANLi crystallizes in a monoclinic mesh (mesh parameters: a = 12.14 Å, b = 9.67 Å, c = 11.94 Å and <x = 90 °, β = 115.93 °, γ = 90 °).

1 H 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.

NMR ⁷ Li (400 MHz; D ₂ 0; δ ppm 0.157

Synthesis of the polymer

2.96 g of ANLi (12.93 mmol) prepared above, 0.77 ml of butadiene diepoxide "BdO" (12.93 mmol) and 10 ml of dimethylformamide DMF are placed in a three-necked flask equipped with a condenser and of a magnetized bar. The reaction mixture is stirred and heated at 55 ° C under an inert atmosphere (flushing with argon) overnight. The reaction mixture is then heated to 100 ° C to complete the polymerization.

At the end of the reaction, the solvent is evaporated under reduced pressure and a pale, stable yellow powder is obtained.

The infrared spectrum of the polymer obtained, noted PI, is represented in FIG. EXAMPLE 2

Preparation of a lithiated PI polymer film in its organized state

Lithium polymer PI

At the end of the reaction, during the synthesis of the polymer P1 as described in Example 1, 0.82 g of lithium hydride LiH (103.44 mmol) is added, ie four equivalents relative to the hydroxyl functions present. The whole is maintained at 70 ° C for about 4 hours. The excess lithiation agent is neutralized by a gradual addition of 1 mL of ethanol. The solvent is removed under reduced pressure to obtain a yellow powder.

The infrared spectrum of the lithiated PI polymer obtained is represented in FIG.

The powder obtained was also characterized by thermogravimetric analysis (ATG) under argon and with a heating rate of 20 ° C / min. The results of the thermogravimetric analysis are shown in FIG.

Preparation of a conductive polymer film in its organized state

A solution of the 100 mg / mL methanol-lithiated PI polymer is prepared.

The deposit is made on different substrates (stainless steel, polyimide (Kapton ^® ), silicon, glass), and covered with a crystallizer.

A film of the conductive polymer in an organized state (critallin) is obtained after one night.

This organization is observable by polarized optical microscopy. FIG. 4 represents, for example, the microscopy obtained by microscopy of the electrolyte film formed on the silicon surface. X-ray diffraction (XRD) analysis (X-ray diffractogram shown in FIG. 5) shows that the polymer in the organized state crystallized in an orthorhombic mesh (mesh parameters: a = 6.49 Å, b = 10.01 Å and c = 4.85 Å).

EXAMPLE 3

Measurement of the ionic conductivity of lithiated PI polymer

The ionic conductivity of the lithiated PI polymer prepared according to Example 2 is evaluated by measuring the contact resistance according to the TLM (Transmission Line Method) method.

Polymer deposits prepared according to Example 2 in an organized (crystalline) state and in amorphous and semi-crystalline states are made on the ionic conductivity measuring device TLM.

Figure 6 shows schematically the structure TLM and the characteristic of the total resistance as a function of the distance between the contacts. The standard method is to deposit on a rectangular sample several contacts (A, B, C and D) in the form of parallel lines. The distance between the contacts is different in order to create a resistance scale. In the case of a homogeneous material, the resistance achieved varies linearly as a function of the distance between two measurement contacts, and it is then possible to extract the value at the origin which represents the sum of the resistances of the two contacts.

The ionic conductivities obtained for the different deposits are presented in Table 1 below, knowing that the electrolyte was not anhydrous.

Table 1

The polymer in its crystalline and hydrated organized state has good ionic conductivity. It can advantageously be used as a solid electrolyte in a lithium battery with an electrochemical couple chosen so that the two materials are in the zone of electrochemical stability of the water. EXAMPLE 4

Preparation of a polymer P2 according to the invention from lithium 4-amino-1-naphthalenesulphonate (ANLi) and 1,4-butanediol diglycidyl ether (BDGE)

The polymer P2 is synthesized according to a protocol similar to that presented in example 1, using 2.38 ml of 1,4-butanediol diglycidyl ether (12.93 mmol) instead of the BdO, 2.96 g of ANLi ( 12.93 mmol) and 10 mL of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. An orange-yellow powder is obtained. The glass transition temperature (Tg) is 84 ° C.

The infrared spectrum of the obtained polymer P2 is represented in FIG.

EXAMPLE 5

Preparation of a lithiated P2 polymer film in its organized state

Lithium polymer P2

The hydroxyl functions of the polymer P2 prepared in Example 4 are lithiated, a protocol similar to that of Example 2, adding at the end of the reaction at the end of the reaction. synthesis of the polymer P2, 0.82 g of lithium hydride LiH (103.44 mmol), ie four equivalents relative to the hydroxyl functions present. The whole is maintained at 70 ° C for about four hours. The excess LiH is neutralized by a gradual addition of 1 mL of ethanol. The solvent is removed under reduced pressure to obtain a yellow powder.

The infrared spectrum of the lithiated P2 polymer obtained is represented in FIG. 9.

Preparation of a conductive polymer film in its organized state

A solution of the metallized P2 polymer in methanol of concentration of 100 mg / mL is prepared.

A film of the conductive polymer in an organized (crystalline) state is obtained after one night.

This organization is observable by polarized optical microscopy.

FIG. 10 represents, for example, the microscopy obtained by microscopy of the electrolyte film formed on the surface of a copper substrate.

X-ray diffraction (XRD) analysis (X-ray diffractogram shown in Figure 11) shows that the polymer in the organized state crystallized in an orthorhombic mesh.

EXAMPLE 6

Preparation of a polymer P3 according to the invention from lithium 4-amino-1-naphthalenesulphonate (ANLi) and resorcinol diglycidyl ether (RDGE)

The polymer P3 is synthesized according to a protocol similar to that presented in Example 1, using 2.87 g of resorcinol diglycidyl ether (12.93 mmol) instead of BdO, 2.96 g of ANLi (12.93 mmol). ) and 10 mL of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. An orange-yellow powder is obtained. The glass transition temperature (Tg) is 136 ° C.

The infrared spectrum of the obtained polymer P3 is shown in FIG.

EXAMPLE 7

Preparation of a lithiated P3 polymer film in its organized state

Lithium polymer P3

The hydroxyl functions of the polymer P3 prepared in Example 6 are lithiated according to a protocol similar to that of Example 2, adding at the end of the reaction during the synthesis of the polymer P3, 0.82 g of lithium hydride LiH (103 44 mmol), ie four equivalents relative to the hydroxyl functions present. The whole is maintained at 70 ° C for about four hours. The excess LiH is neutralized by a gradual addition of 1 mL of ethanol. The solvent is removed under reduced pressure to obtain a yellow powder.

Preparation of a conductive polymer P3 film in its organized state

A solution of the polymerized P3 polymer in methanol concentration of 100 mg / mL is prepared. The deposit is made on different substrates (stainless steel, polyimide (Kapton), silicon, glass), and covered with a crystallizer.

A film of the conductive polymer, in an organized (crystalline) state, is obtained after one night and is observable by polarized light microscopy.

EXAMPLE 8

Preparation of a polymer P4 according to the invention starting from 4-amino-1-naphthalenesulphonic acid and butadiene diepoxide

2.89 g of 4-amino-1-naphthalenesulfonic acid ANH (12.93 mmol), 0.77 ml of butadiene diepoxide BdO (12.93 mmol) and 10 ml of dimethylformamide DMF are placed in a three-necked flask equipped with a refrigerant and a magnetized bar. The reaction mixture is stirred and heated at 55 ° C. under an inert atmosphere (flushing with an argon stream) until a homogeneous mixture is obtained. The reaction mixture is then heated to 100 ° C to complete the polymerization. At the end of the reaction, the solvent is evaporated under reduced pressure and a pale, stable yellow powder is obtained.

The polymer P4 in its organized state can be implemented as a proton conductive electrolyte, for example in a proton exchange membrane fuel cell (PEMFC) or a low temperature electrolyser.

EXAMPLE 9

Preparation of a polymer P5 according to the invention starting from 4-amino-1-naphthalenesulphonic acid and 1,4-butanediol diglycidyl ether (BDGE)

The polymer P5 is synthesized according to a protocol similar to that of Example 8 above, using 2.38 ml of 1,4-butanediol diglycidyl ether BDGE (12.93 mmol) in place of the BdO, 2.89 g of ANH (12.93 mmol) and 10 mL of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. An orange-yellow powder is obtained.

The polymer P5 in its organized state can be implemented as a protonic conductive electrolyte.

EXAMPLE 10

Preparation of a polymer P6 according to the invention starting from 4-amino-1-naphthalenesulphonic acid and resorcinol diglycidyl ether (RDGE)

The polymer P6 is synthesized according to a protocol similar to that of Example 8 above, using 2.87 g of resorcinol diglycidyl ether RDGE (12.93 mmol) in place of BdO, 2.89 g of ANH (12.93 mmol). 93 mmol) and 10 mL of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. An orange-yellow powder is obtained.

The infrared spectrum of the resulting polymer P6 is shown in Figure 14. The glass transition temperature (Tg) is 37 ° C.

The polymer P6 in its organized state can be implemented as a protonic conductive electrolyte. EXAMPLE 11

Preparation of a polymer P7 according to the invention from lithium 4-amino-1-naphthalenesulphonate (ANLi) and poly (dimethylsiloxane) diglycidyl ether (PDMSDGE)

The polymer P7 is synthesized according to a protocol similar to that presented in example 1, using 11.59 g of poly (dimethylsiloxane) diglycidyl ether (11.83 mmol) in place of the BdO, 2.71 g of ANLi (11 83 mmol) and 15 mL of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. A brown powder is obtained.

The infrared spectrum of the obtained polymer P7 is represented in FIG.

The powder obtained was also characterized by thermogravimetric analysis (ATG) under argon and with a heating rate of 20 ° C / min. The results of the thermogravimetric analysis are shown in FIG. EXAMPLE 12

Preparation of a polymer P8 according to the invention starting from 4-amino-1-naphthalenesulphonic acid and poly (dimethylsiloxane) diglycidyl ether (PDMSDGE)

The polymer P8 is synthesized according to a protocol similar to that of Example 8 above, using 11.39 g of poly (dimethylsiloxane) diglycidyl ether PDMSDGE (11.62 mmol) in place of BdO, 2.59 g of ANH (11.62 mmol) and 10 mL of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. A viscous yellow paste is obtained.

The infrared spectrum of the obtained polymer P8 is represented in FIG. 17.

The polymer obtained was also characterized by thermogravimetric analysis (ATG), under argon and with a heating rate of 20 ° C / min. The results of the thermogravimetric analysis are shown in FIG. 18. The glass transition temperature (Tg) is 24.degree.

The polymer P8 in its organized state can be implemented as a protonic conductive electrolyte. EXAMPLE 13

Measurement of the ionic conductivity of the polymer P2

The ionic conductivity of the polymer P2 is evaluated by measuring the resistance of two interdigitated gold electrodes (NOVOCONTROL) over a temperature range from 100 ° C to 215 ° C.

The polymer powder P2 is deposited so as to cover the device. To ensure good impregnation, the polymer is maintained for 15 min at 150 ° C. The images obtained by polarized optical microscope are represented in FIG. 19. Transition

Polymer state Mesophase -> Isotropic

Glassy -> Mesophase

Temperature of

50,210

transition (° C)

Table 2

The ionic conductivities obtained for the various deposits are presented in FIG.

The polymer in its organized state has good ionic conductivity. It can advantageously be used as a solid electrolyte in a lithium battery.

EXAMPLE 14

Synthesis of lithium 4-amino-1-naphthalenetrifluorosulfonamide (ANTFSILi) • Step 1: protection of the primary amine (Pro-ANH)

4.77 g of 4-amino-1-naphthalenesulfonic acid ANH (20.73 mmol), 3.4 ml of phthaloyl chloride (21.25 mmol) and 30 ml of pyridine are placed in a three-necked flask equipped with a refrigerant and a magnet bar. The reaction mixture is stirred and heated at 100 ° C under an inert atmosphere (flushing with argon) for 17h. At the end of the reaction, the solvent is evaporated under reduced pressure. A pale yellow precipitate is obtained after recrystallization from methanol. (R = 42%)

1H NMR (200 MHz, DMSO-d6, 300 K): δ ppm 8.94 (m, 3H); 8.58 (m, 1H); 7.74 (m, 12H); Step 2: synthesis of thionyl chloride derivative (Pro-ANS0 ₂ Cl)

2.35 g of Pro-ANH (5.43 mmol), 0.7 ml of thionyl chloride (9.68 mmol) and 11 ml of dimethylformamide (DMF) are placed in a three-necked flask equipped with a condenser and a magnetized bar. The reaction mixture is stirred for 3h at room temperature under an inert atmosphere (scanning with a stream of argon). The reaction is stopped by pouring the reaction medium into cold distilled water. After filtration and drying, a white precipitate is obtained (R = 100%)

1 H NMR (400 MHz, DMSO-d6, 300 K): δ ppm 8.94 (dd, 1H); 8.01 (m, 5H); 7.75 (m, 1H); 7.57 (m, 3H);

• Step 3: synthesis of the

403.5 mg of Pro-ANS0 ₂ Cl (1.08 mmol), 163.7 mg of trifluoromethanesulfonamide (1.08 mmol), 11.2 mg of 4- (dimethylamino) pyridine (DMAP), 0.23 g of triethylamine ( TEA) and 5 ml of dichloromethane (CH ₂ C1 ₂ ) are placed in a three-necked flask equipped with a condenser and a magnetic bar. The mixture The reaction mixture is stirred for 16 hours at room temperature under an inert atmosphere (scanning with a stream of argon). After extraction, 2 * 5mL NaHCO ₃ 4% and 1 * 5mL of 1M HCl, the organic phase is evaporated. A yellow oil is then obtained.

The infrared spectrum of the product obtained is shown in FIG.

· Step 4: Synthesis' ANTFSI-Li

Li ⁺

522.72 mg of Pro-ANTFSA (1.08 mmol), 163.7 mg of trifluoromethanesulfonamide (1.08 mmol), 1.2 mL of hydrazine monohydrate and 8.6 mL of methanol are placed in a three-necked flask equipped with a refrigerant and a magnetized bar. The reaction mixture is stirred for 17 hours at room temperature under an inert atmosphere (scanning with a stream of argon). The precipitate obtained is filtered and washed with methanol. The filtrate is evaporated.

The product obtained is solubilized in 20 ml of distilled water and 52 mg (1.23 mmol) of lithium hydroxide hydrate. PH monitoring was performed during lithiation and presented in Figure 22.

The product is obtained after evaporation of the solvent and several washings with ethanol.

EXAMPLE 15

Preparation of a polymer P9 according to the invention from lithium 4-amino-1-naphthalenesulphonate (ANLi) and diglycidyl ether (DGE)

The polymer P9 is synthesized according to a protocol similar to that shown in Example 1, using 100 mg of diglycidyl ether (0.77 mmol) in place of the DGE, 0.176 g of ANLi (0.176 mmol) and 5 ml of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. A light brown powder is obtained.

The infrared spectrum of the obtained polymer P7 is represented in FIG.

The powder obtained was also characterized by thermogravimetric analysis (ATG) under argon and with a heating rate of 10 ° C./min. The results of the thermogravimetric analysis are shown in Figure 24. EXAMPLE 16

Preparation of a polymer P10 according to the invention from lithium 4-amino-1-naphthalenedisulfonate (DiANLi) and butanedioldiglycidyl ether (BDGE)

Synthesis of lithium 4-amino-1-naphthalenedisulfonate (DiANLi)

0.483 g of 4-amino-1,7-naphthalenesulphonic acid (DiANH) and 0.067 g of lithium hydroxide monohydrate (LiOH, H ₂ 0) are added in 10 ml of distilled water. The reaction medium is stirred for 1 night at room temperature. The excess of ANH is removed by filtration. The filtrate is then concentrated by evaporation of the solvent under reduced pressure. After two washes with ethanol, an orange powder is obtained.

Synthesis of the polymer

Polymer P10 is synthesized according to a protocol similar to that shown in Example 1, using 0.16 ml of 1,4-butanediol diglycidyl ether (0.85 mmol) in place of BdO, 0.2685 g of DiANLi (0). 85 mmol) and 5 mL of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. A brown powder is obtained.

The infrared spectrum of the obtained polymer P10 is shown in FIG. The powder obtained was also characterized by thermogravimetric analysis (ATG) under argon and with a heating rate of 10 ° C./min. The results of the thermogravimetric analysis are shown in FIG.

EXAMPLE 17

Preparation of a Ply Polymer According to the Invention from Lithium 5-naphthalenesulphonate and Butadiene Diepoxide

Synthesis of lithium 5-amino-1-naphthalenesulphonate (AN'Li)

24.44 g of 5-amino-1-naphthalenesulphonic acid (AN'H) and 4.13 g of lithium hydroxide monohydrate (LiOH, H ₂ O) are added in 500 ml of distilled water. The reaction medium is stirred for 1 night at room temperature. The excess of AN'H is removed by filtration. The filtrate is then concentrated by evaporation of the solvent under reduced pressure. After two washes with ethanol, a violet powder is obtained.

1H NMR (400 MHz, pyridine-d6, 300 K): δ ppm 9.2 (d, 1H); 8, 5 (d, 1H); 7.3 (m, 4H); 5.92 (s, 2H);

Synthesis of the polymer

Polymer P10 is synthesized according to a protocol similar to that shown in Example 1, using 2.37 ml of 1,4-butanediol diglycidyl ether (12.25 mmol) instead of BdO, 2.81 g of AN'Li (12.25 mmol) and 15 mL of DMF. The temperature is set at 70 ° C. at the beginning of the reaction. A dark brown powder is obtained.

The infrared spectrum of the polymer obtained, denoted Pl i, is represented in FIG. 27.

The powder obtained was also characterized by thermogravimetric analysis (ATG) under argon and with a heating rate of 10 ° C./min. The results of the thermogravimetric analysis are shown in FIG.

EXAMPLE 18

Measurement of phase transitions by POM of polymer P7

The P7 polymer powder is deposited on a microscope glass plate. The sample is placed in a platinum and we observed the state of it at different temperatures. Table 3 shows the transitions observed. The images obtained by polarized optical microscope are represented in FIG.

Table 3

EXAMPLE 19

Measuring the ionic conductivity of polymers P

The ionic conductivity of the P polymers was evaluated by measuring the resistance of two aluminum plates of a rheometer over a temperature range of 100 ° C to 215 ° C.

The results obtained are shown in Figure 28.

Claims

A compound comprising at least one entity of formula (I):

in which :

p is an integer ranging from 1 to 10, preferentially from 1 to 4;

G represents:

*

Ar

(a) a group ^DD , in which:

⁰ - □ represents a bond with Γ spacer E; and

⁰ - * represents one or more bonds with said anion (s) A ^{x ~} ; □ - X-Ar-Χ ^ π

or (b) a group, wherein:

⁰ - □ represents a bond with spacer E; and

⁰ - * represents one or more bonds with said anion (s) A ^{x ~} ;

⁰ Ar is as defined previously;

the said anion (s) A ^{x ~} being covalently bound to the polycyclic group Ar.

2. Compound according to the preceding claim, said compound being a polymer comprising, or even being formed, monomeric units of formula (Γ):

in which G, E, A ^{x ~} , C ^{x +} and p are as defined in claim 1.

3. Compound according to claim 1 or 2, said compound being a polymer comprising, or even being formed, monomeric units of formula (II):

C ^{x +} '

^AX 'p

Ar

in which E, Ar, A ^{x ~} , C ^{x +} and p are as defined in claim 1.

4. Compound according to any one of the preceding claims, characterized in that Ar has one of the following cyclic backbones:

5. Compound according to any one of the preceding claims, characterized in that Ar is an aromatic bicyclic group, in particular having a naphthalene aromatic skeleton, and more particularly Ar is a naphthalene group.

6. Compound according to any one of the preceding claims, characterized in that E is a linear or branched aliphatic chain, saturated or unsaturated, with at least two covalent bonds, said chain being optionally interrupted by a or more heteroatom (s), in particular S, O or N, with one or more metalloids, for example silicon, and / or with one or more (hetero) rings, aromatic or otherwise, of 4 to 6 members; said chain being optionally substituted by one or more fluorine atoms and / or by one or more R 1 groups,

R 1 represents a group chosen from a hydroxyl group, optionally in protonated form -O ^" C ⁺ , an -NH ₂ group and an oxo group.

7. Compound according to any one of the preceding claims, characterized in that E represents a saturated linear aliphatic chain C ₄ to C ₂ o, said chain being optionally interrupted by one or more heteroatoms, in particular one or more atoms of oxygen, and / or by one or more aromatic or non-aromatic 4- to 6-membered rings, in particular one or more benzene rings, said chain being optionally substituted by one or more hydroxyl groups, preferably in protonated form -O ^" C ⁺ .

8. Compound according to any one of the preceding claims, characterized in that n is between 2 and 1500, in particular between 2 and 300.

9. Compound according to any one of the preceding claims, characterized in that A ^{x ~} is a sulfonate anion or a trifluoromethylsulfonylimide anion, in particular a sulfonate anion.

10. Compound according to any one of the preceding claims, characterized in that C ^{x +} is the proton H ⁺ or the cation Li ⁺ .

11. A compound according to any one of the preceding claims, said compound being a polymer comprising, or even being formed, monomeric units of formula (III):

wherein E, A ^{x ~} and C ^x are as defined in any one of claims 1 to 10.

12. Use of at least one compound as defined in any one of claims 1 to 11, in the organized state, as solid electrolyte in an electrochemical system.

13. Solid electrolyte comprising, or being formed, one or more compounds as defined according to any one of claims 1 to 11, in the organized state.

14. Electrolyte according to the preceding claim, characterized in that it has an ionic conductivity at 120 ° C greater than or equal to 10 ^"9 S / cm, in particular between 10 ^{" 8} and 5.10 ⁵ S / cm.

15. Electrolyte according to claim 13 or 14, characterized in that it has an ionic conductivity at 200 ° C greater than or equal to 10 ^{~ 7} S / cm, in particular between 10 ^{~ 7} and 10 ^"3 S / cm.

A method of forming a film comprising a solid electrolyte at the surface of a substrate, comprising at least the steps of:

(a1) having a solution comprising at least one compound as defined according to any one of claims 1 to 11, in a polar solvent, in particular Ν, Ν-dimethylformamide, dimethylacetamide, monoalcohols, for example methanol, the water ;

(b1) depositing said solution of step (a1) at the surface of said substrate; and (c) evaporating the solvent under conditions conducive to forming a film comprising the solid electrolyte formed from the compound of formula (I) in its organized state.

A method of forming a solid electrolyte film, self-supported or supported by a substrate, comprising at least the steps of:

(a2) having a powder formed of a compound as defined in any one of claims 1 to 11;

(c2) spreading said electrolyte film, optionally on the surface of a substrate.

18. The method of claim 16 or 17, wherein said film comprising the solid electrolyte has a thickness between 5 and 50 μιη, in particular 5 μιη.

The method of any one of claims 16 to 18, said method further comprising one or more subsequent steps of exposing said formed film to an electric field, magnetic field, or ionizing radiation, particularly photonic radiation.

20. Composite electrode for an electrochemical system, in particular a positive electrode of a lithium battery, comprising at least one solid electrolyte as defined according to any one of Claims 13 to 15.

An electrochemical system comprising a solid electrolyte as defined in any one of claims 13 to 15.

The electrochemical system of claim 21 comprising:

a solid electrolyte film as defined in any one of claims 13 to 15 or as obtained according to the process defined according to any one of claims 16 to 19, serving as both an ionic conductor and a separator between the positive and negative electrodes, and

at least one composite electrode as defined in claim 20.

23. System according to claim 21 or 22, characterized in that it is a battery, in particular a lithium battery.