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  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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  • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
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  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
• • H—ELECTRICITY
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  • H01M10/00—Secondary cells; Manufacture thereof
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  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/137—Electrodes based on electro-active polymers
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  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
• • H—ELECTRICITY
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  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
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  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• 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.
• 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.
• 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.
• electrolyte used 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.
• the electrolytes of the electrochemical systems are in liquid, gelled or solid 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.
• conventional supercapacity electrolytes are composed of an organic salt (typically a tetraethylammonium tetrafluoroborate salt and 4 N-BF 4 ) dissolved in acetonitrile.
• organic salt typically a tetraethylammonium tetrafluoroborate salt and 4 N-BF 4
• 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.
• 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 ®.
• 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.
• 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.
• first ion conductive block for example polyethylene oxide
• second block non-conductive and immiscible with the first block to ensure a micro-phase separation
• micro-phase separation for example of the polyalkylacrylate or polydimethylsiloxane type.
• anion for example carboxylate, sulfonate or phosphate
• the present invention aims precisely to propose new solid electrolytes, cationic or protonic conductors, having improved ionic conductivity and electrochemical stability.
• 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;
• G represents:
• 0 X is N, P or Si-R, with R representing a hydrogen atom or a Ci_4 alkyl group,
• 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 ⁇ spacer E; and 0 - * represents one or more bonds with said anion (s) A x ⁇ ;
• 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;
• 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.
• 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.
• the organized state still corresponds to the state of the thermodynamically stable compound at a given temperature below its melting or decomposition temperature.
• the organized state may be a crystalline state of the compounds according to the invention.
• 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.
• solid electrolyte 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).
• generators for example lithium batteries
• electrochemical conversion systems for example proton exchange membrane fuel cells ( PEMFC).
• PEMFC proton exchange membrane fuel cells
• 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.
• 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.
• the solid electrolyte according to the invention in addition to ensuring the passage of the ions from one electrode to the other, also serves as separator, for electronically isolating the two electrodes of the electrochemical system.
• 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.
• the compounds according to the invention comprise at least one entity of formula (I) below:
• 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;
• 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;
• G represents:
• 0 X is N, P or Si-R, with R representing a hydrogen atom or a Ci_4 alkyl group,
• 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 ⁇ spacer E
• 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
• 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.
• 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.
• 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.
• the alkaline earth metal is magnesium or potassium.
• organic spacer E 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.
• n in formula (I) above may be between 2 and 1500, in particular between 2 and 300.
• the compound of the invention may be a (co) polymer comprising at least one entity of formula (I) defined above.
• 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 ⁇ .
• the compounds according to the invention are polymers comprising, or even being formed, monomeric units of formula (F) below:
• 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.
• 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.
• the polycyclic groups, Ar are side groups of the main chain of the compound according to the invention.
• X is N, P or Si-R, with R representing a hydrogen atom or a Ci_4 alkyl group; preferably X is N;
• 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 one or more bonds with said anion (s) A x ⁇ ; the said anion (s) A x ⁇ being covalently bound to the polycyclic group Ar.
• the compounds according to the invention are polymers comprising, if not being formed, monomeric units of formula (II) below:
• E, Ar, A x ⁇ , C x + and p are as previously defined or described more precisely below.
• the polycyclic groups, Ar are integrated in the main chain of the compound according to the invention.
• 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;
• 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;
• Ar is a polycyclic group comprising from 2 to 4 rings, with in particular at least one of the rings being aromatic.
• Ar is an aromatic polycyclic group formed from 2 to 6 aromatic rings.
• Ar may have one of the following polycyclic skeletons:
• 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.
• Ar is an aromatic bicyclic group, in particular having an aromatic naphthalene backbone.
• Ar is a naphthalene group.
• the compounds according to the invention are polymers comprising, or even being formed, monomeric units of formula (III) below:
• E in formula (I) 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.
• 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.
• 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.
• s heteroatoms
• metalloids for example silicon
• R 1 groups represents a group chosen from a hydroxyl group, optionally in protonated form -O " C + , an -NH 2 group and an oxo group.
• R 1 is a hydroxyl group, optionally in protonated form -O " C + .
• 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.
• 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.
• 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 + .
• 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
• C + cations immobilized at the spacer do not participate in the charge transfer.
• the anion A x ⁇ may be more particularly selected from sulfonate anions (SO3) and trifluoromethylsulfonylimide (TFSI).
• a x ⁇ is a sulfonate anion.
• C x represents the proton H.
• such compounds can be advantageously used as solid electrolyte in a lithium battery.
• C x + represents the Li + cation.
• PEMFC proton exchange membrane fuel cell
• low temperature electrolyser a proton exchange membrane fuel cell
• polymers comprising, in particular constituted, monomeric units of formula (IV) below:
• 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.
• 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)
• 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,
• 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.
• 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 (II) above can be obtained via a nucleophilic addition reaction between a compound of formula (II) above.
• spacer E and a precursor of the spacer E, having two identical electrophilic functions, for example epoxide functional groups.
• Nu ' identical or different, represent mono-functional nucleophilic functions, in particular chosen from hydroxyl, thiol or secondary amine functions,
• 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.
• 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.
• 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.
• 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.
• 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.
• 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).
• the solid electrolyte according to the invention can be obtained by controlled evaporation.
• 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:
• step (b1) depositing said solution of step (a1) at the surface of said substrate;
• the polar solvent in step (a1) may for example be the
• DMF ⁇ , ⁇ -dimethylformamide
• DMAc dimethylacetamide
• monoalcohols including methanol, water.
• 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.
• 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.
• 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.
• the method for preparing a solid electrolyte film can implement at least the steps consisting in:
• 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 ⁇ , in particular about 5 ⁇ .
• 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.
• a fuel cell for example a proton exchange membrane fuel cell (PEMFC)
• PEMFC proton exchange membrane fuel cell
• primary or secondary battery for example a lithium, sodium, magnesium, potassium or calcium battery
• a lithium-air, lithium-sulfur accumulator for example a lithium, sodium, magnesium, potassium or calcium battery.
• the solid electrolyte is implemented in a battery, in particular a lithium battery.
• An electrochemical system 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.
• 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.
• 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 ⁇ , in particular of approximately 5 ⁇ .
• 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.
• 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 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.
• At least one of the electrodes of the electrochemical system according to the invention 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.
• 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.
• 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.
• the cathode can be a composite electrode.
• 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.
• a composite electrode that can be used for example as a positive electrode in a lithium battery can be formed via the following steps:
• 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).
• PVDF polyvinylidene fluoride
• SBR styrene-butadiene rubber
• the dispersion 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 .
• 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 ⁇ and 400 ⁇ , in particular between 100 ⁇ and 250 ⁇ .
• the invention further relates, in another of its aspects, to an electrochemical system comprising:
• At least one composite electrode (the positive electrode and / or the negative electrode) as described above.
• 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
• 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;
• FIG. 13 ATG thermogravimetric analysis diagram obtained for the polymer P3 powder formed according to Example 6;
• FIG. 16 ATG thermogravimetric analysis diagram obtained for the P7 polymer powder formed according to Example 11;
• 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.
• 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.
• thermogravimetric analysis ATG
• thermogravimetric analysis ATG
• 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.
• FIG. 4 represents, for example, the microscopy obtained by microscopy of the electrolyte film formed on the silicon surface.
• 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 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.
• 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.
• thermogravimetric analysis ATG
• thermogravimetric analysis ATG
• 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.
• 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.
• a solution of the metallized P2 polymer in methanol of 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.
• 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 shows that the polymer in the organized state crystallized in an orthorhombic mesh.
• 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.
• thermogravimetric analysis ATG
• thermogravimetric analysis ATG
• 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.
• 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.
• 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.
• PEMFC proton exchange membrane fuel cell
• low temperature electrolyser low temperature electrolyser
• 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.
• 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.
• 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.
• thermogravimetric analysis ATG
• thermogravimetric analysis ATG
• 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.
• 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
• the polymer in its organized state has good ionic conductivity. It can advantageously be used as a solid electrolyte in a lithium battery.
• 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.
• 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.
• thermogravimetric analysis ACG under argon and with a heating rate of 10 ° C./min. The results of the thermogravimetric analysis are shown in Figure 24.
• 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.
• 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.
• thermogravimetric analysis ATG
• argon argon
• heating rate 10 ° C./min.
• FIG. 1 The results of the thermogravimetric analysis are shown in FIG.
• 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.
• 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.

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