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  • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
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• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
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  • Y02E60/13—Energy storage using capacitors
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  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/60—Other road transportation technologies with climate change mitigation effect
  • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

• the present invention relates to the field of lithium secondary batteries. More particularly, it relates to the use of new electronically conductive polymers as an active electrode material for secondary lithium batteries, in particular for lithium-ion batteries.
• Lithium batteries are increasingly being used as stand-alone power sources, especially in portable equipment, where they are gradually replacing nickel-cadmium (NiCd) and nickel-metal hydride (NiMH) batteries. This evolution is explained by the continuous improvement of the performance of lithium batteries, thus giving them much higher energy densities than those proposed by the NiCd and NiMH sectors. Lithium batteries find many applications, especially in the new technologies of information and communication (NICT), medical devices, electric vehicles, energy storage of photovoltaic cells, etc.
• NTI information and communication
• electrochemical lithium generators function conventionally on the principle of insertion or deinsertion (or intercalation-deintercalation) of lithium on at least one electrode.
• the Li + cations are thus back and forth between the electrodes, positive and negative respectively, at each charge and discharge of the accumulator.
• the active material of the positive electrode is capable of releasing lithium ions at the time of charging and incorporating lithium ions at the time of discharge.
• the active compounds of electrodes used in commercial accumulators are, for the positive electrode, 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 .
• the negative electrode is generally carbon (graphite, coke, etc.) or possibly spinel Li 4 Ti 5 0i 2 or an alloying metal with lithium (Sn, Si, etc.).
• the most commonly used polymers are polyanilines, polypyrroles, polymers having on their chain a component bearing a disulfide bridge, or else proton conductive compounds containing at least one heterocycle with a nitrogen atom. These active materials are mainly used for primary lithium-ion batteries, that is non-rechargeable batteries.
• US Pat. No. 7,651,647 proposes the use of a mixture of an active material such as vanadium-silver oxide or fluorinated carbon and of a conductive polymer chosen from polyaniline and polydioxythiophene. and their combination, for the manufacture of a positive electrode of an electrochemical cell.
• an active material such as vanadium-silver oxide or fluorinated carbon
• a conductive polymer chosen from polyaniline and polydioxythiophene
• JP 2010-1802854 describes the preparation of poly (methylmethacrylate) polymers grafted with nitroxide functions such as 2,2 groups, 6,6-tetramethyl-piperidinyl-N-oxy (TEMPO).
• TEMPO 6,6-tetramethyl-piperidinyl-N-oxy
• these graft polymers in lithium secondary batteries requires the joint implementation of large amounts of conventional electronic conductors, such as carbon black, generally between 20% and 70% by weight, to allow the extraction of electrons from the active material.
• electronic conductors such as carbon black
• the addition of such amounts of electronic conductors is unfortunately to the detriment of the mass or volume energy density of the electrode, and makes any industrial application very expensive.
• complementary binders is necessary to ensure the adhesion of the polymer material on the current collector and a good mechanical strength of the electrode.
• these graft polymers are formed by grafting the nitroxide functions on the monomers, prior to the polymerization, which makes the reaction steps delicate and leads to poor yields.
• the present invention aims at providing novel polymers that can be used as electrode material for lithium secondary batteries, and that make it possible in particular to overcome the aforementioned drawbacks.
• a polymer having a linear backbone chosen from homopolymers belonging to the family of polyfluorenes, polycarbazoles, polyanilines, polyphenylenes, polyisothionaphthenes, polyacetylenes, polyphenylenevinylenes, and their copolymers, said backbone bearing at least one side group having at least one nitroxide function.
• lateral means that said group is arranged to include a group during or "graft" at the level of the linear backbone.
• graft polymers or “polymers functionalised” by said groups.
• side groups or “grafts” will more simply be used to denote lateral groups having at least one nitroxide function.
• Such electronically conductive graft polymers are particularly advantageous as an electrode active material for secondary lithium batteries, the grafted nitroxide functions ensuring the reversible complexation of Li + ions.
• nitroxide function is meant the radical form NO ' .
• the invention also relates, in another of its aspects, the use of such polymers as electrode material. It also relates to such an electrode material and the electrode thus formed.
• the use of graft polymers according to the invention as electrode material proves to be advantageous for several reasons.
• the electrodes formed according to the invention can be used for the production of lithium batteries having very short charge and recharge times (of the order of 1 to 10 minutes), and can therefore advantageously be used. implemented to obtain a strong current in a short time.
• the use of the polymers of the invention to form efficient electrodes in lithium secondary battery devices does not require the implementation of additional electronic conductors and thus reduces the amount of such additional electronic conductors. or even to completely get rid of it.
• the polymers of the invention can act both as charge extractors to the current collector of the electrode, but also as binders.
• the use of the polymers according to the invention makes it possible to reduce the quantity of additional binders to be introduced, or even to completely avoid the use of additional binders.
• the graft polymers of the invention by grafting the carrier groups of one or more nitroxide functions directly on the unfunctionalized polymers already formed.
• This method of preparation is particularly advantageous, compared to the process usually used in which the grafting is carried out on the monomers before polymerization, and leads to improved reaction yields, which makes it possible to optimize the process for preparing the electrode material. and therefore the manufacturing steps of the electrodes and the resulting electrochemical cells.
• the polymers according to the invention have a linear backbone chosen from homopolymers belonging to the family of polyfluorenes, polycarbazoles, polyanilines, polyphenylenes, polyisothionaphthenes, polyacetylenes, polyphenylenevinylenes, and their copolymers.
• said linear skeleton is chosen from homopolymers belonging to the family of polyfluorenes and polycarbazoles, and their copolymers.
• It may be in particular a linear skeleton formed in whole or part of a polyfluorene.
• the polymers of the invention have a linear backbone formed of a polyfluorene.
• the polymers of the invention have lateral groups, also called grafts, having at least one nitroxide function (NO).
• the polymers according to the invention have an electroactivity potential compatible with the redox potential of the nitroxide function.
• electroactivity potential of the polymer is meant the potential at which the doping reaction corresponding to the creation of a negative charge for n doping or positive for p doping, delocalized on several monomer units, takes place. This reaction is reversible (possibility of dedoping) and greatly improves the electronic conductivity of the polymer.
• the lateral groups carrying at least one nitroxide function may have one of the following structures (G1) to (G8):
• the grafts carried by a polymer according to the invention may be identical or different.
• At least some or all of said side groups have at least two nitroxide functions, in particular possess two nitroxide functions.
• the person skilled in the art is able to choose the nature of the grafts to be used, in particular with regard to the number of nitroxide functions per graft, to obtain the molar grafting rate in nitroxide functions of said desired polymer.
• the polymers according to the invention have a molar grafting rate of nitroxide functions ranging from 1 to 800%, preferably from 50 to 200%.
• the polymers according to the invention have the following general structure (I): in which :
• - A and B represent, independently of one another, a hydrogen atom, a halogen atom, in particular bromine, an acetylenic function (for example ethynyl), a boronic acid function (-B (OH) 2 ) or borane (for example pinacolborane (-B (O 2 C 2 H 4 ))), a stannic function (for example -SnR 3 , with R representing an alkyl), a zinc group (for example -ZnX with X being a halogen) or a magnesium group (for example -MgX with X being a halogen atom);
• - (Zi) m - and - (Z 2 ) p - represent the sequence of one or more monomers chosen from carbazole, aniline, phenylene, isothionaphthene, acetylene and phenylenevinylene monomers; - (Zi) m - being in position 5, 6, 7 or 8 of the fluorene, - (Z 2 ) p - being in position 1, 2, 3 or 4 of the fluorene;
• R 1 and R 2 represents * -Y (G) t , with:
• Y is a covalent bond; a linear or branched, saturated or unsaturated (Ci-C 5 ) alkyl group optionally interrupted by one or more heteroatoms such as S, O, N or by one or more ether, ester or amide functions;
• Y represents a linear or branched, saturated or unsaturated (C 1 -C 5) alkyl group optionally interrupted by one or more heteroatoms such as S, O, N or by one or more ether or ester functional groups; or amide; -O-; -COO- or -CONH-;
• G representing a group having at least one nitroxide function, in particular chosen from the structures (G1) to (G8) defined above;
• R 1 and R 2 represents -Y (G) t which is identical or different, or a hydrogen atom; m and p represent integers ranging from 0 to 50000; and
• R 1 represents a group -Y (G) t with t being equal to 1, Y representing a covalent bond, and G being chosen from the structures (G 1) to (G 8) defined above, in particular representing a group TEMPO (structure (Gl)).
• the polymers of the invention may be polyfluorenes bearing side groups having at least one nitroxide function.
• a and B represent, independently of one another, a hydrogen atom or a halogen atom, in particular bromine;
• Ri represents a group * -Y (G) t with t being equal to 1;
• Y representing a covalent bond, and G being selected from the structures (G1) to (G8) as defined above, in particular (G1);
• R 2 represents H;
• m and p are 0 and n is an integer from 2 to 50000.
• Such polymers may more particularly have a degree of polymerization ranging from 5 to 5000, preferably from 10 to 100.
• the polymers of the invention may be crosslinked.
• crosslinked polymers means polymers resulting from the use, during the polymerization, of a crosslinking or branching agent, that is to say having several polymerizable functions, preferably bifunctionalized.
• the polymers of the invention may comprise, in addition to said lateral groups having one or more nitroxide functions, one or more additional lateral groups, for example linear (C 1 -C 5) alkyl groups or branched, saturated or unsaturated, optionally interrupted by one or more heteroatom (s) such as S, O, N or by one or more functions ether, ester or amide; -O-; -COO- or -CONH.
• additional lateral groups for example linear (C 1 -C 5) alkyl groups or branched, saturated or unsaturated, optionally interrupted by one or more heteroatom (s) such as S, O, N or by one or more functions ether, ester or amide; -O-; -COO- or -CONH.
• the polymers according to the invention can be prepared according to two alternative routes:
• the polymers according to the invention can be prepared according to a process comprising at least the steps consisting in:
• the polymer of step (a) can be prepared, prior to its implementation in the method of the invention, according to polymerization methods known to those skilled in the art.
• polymers of structure (I) as defined above can be prepared according to a process comprising the bringing together of a polymer having the following structure (II):
• A, B, Z ls Z 2, m, n and p are as defined above;
• X represents a leaving group, in particular a halogen function, a mesylate or tosylate group; and R 3 is H;
• X and R 3 represent groups capable of interacting together, in the presence of a transition metal catalyst, according to a coupling reaction, to form a CC bond;
• polymers of formula ( ⁇ ) defined above may be particularly prepared by grafting compounds of formula:
• X represents a leaving group, in particular a halogen functional group, a mesylate or tosylate group
• the grafting of the groups according to the invention on said polymer can be carried out via a coupling reaction between said substituents R 3 and X to lead to the formation of a DC bond, in the presence a transition metal catalyst.
• one of the substituents X and R 3 can represent a halogen atom, the other of X and R 3 representing a borane, boric acid, stannic or zinc function, said coupling reaction being catalyzed by a complex of palladium.
• one of X and R 3 represents a halogen, the other representing a borane or boric acid function, the coupling reaction being carried out in the presence of a palladium complex (reaction known under term "Suzuki coupling").
• one of X and R 3 represents a halogen, the other represents a stannic function, the coupling reaction being carried out in the presence of a palladium complex (reaction known under the name " Stille coupling ").
• one of X and R 3 represents a halogen, the other represents a zinc function, the coupling reaction being carried out in the presence of a palladium complex (reaction known under the name "Negishi coupling").
• the polymers according to the invention can be prepared according to a process comprising at least the steps consisting in:
• the monomers of step (c) may be prepared beforehand by grafting methods known to those skilled in the art, as illustrated in Example 2.
• polymers of structure (I) as defined above can be prepared by polymerization of monomers of formula (III) below:
• R 1, R 2 , A and B are as previously defined, where A is at the 5, 6, 7 or 8 position of the fluorene, B is in the 1, 2, 3 or 4 position of the polyfluroene to form a structural polymer ( I) as defined above.
• the polymers of formula ( ⁇ ) defined above can be prepared by polymerization of monomers of formula ( ⁇ ):
• the polymer according to the invention can be implemented as an electrode active material.
• the invention thus relates to an electrode active material comprising at least one polymer as defined above.
• the electrode material may be prepared in the form of a powder.
• the electrode material may comprise a polymer or mixture of polymers according to the invention. It may comprise, in addition to the polymer or polymers of the invention, one or more additional compounds conventionally used, for example a binder or a conductive additive.
• the invention relates to an electrode comprising an electrode material as described above.
• the electrode material represents from 5 to 100% by weight of the total weight of the electrode, in particular more than 70% by weight, and more particularly from 80 to 100% by weight, relative to the total weight of the electrode. said electrode.
• An electrode according to the invention can be used as a positive electrode or as a negative electrode, in particular a lithium generator.
• an electrode according to the invention may comprise a current collector on which said electrode active material is applied, for example by the techniques developed below.
• the electrode may further comprise one or more additive (s) conductor (s) electronic (s) and / or one or more binder (s).
• the electronic conductive additive (s) may be chosen from carbon fibers, carbon black, carbon nanotubes and their analogues.
• the one or more electronic conductive additives may be present in an amount of less than or equal to 20% by weight relative to the total weight of said electrode, preferably less than or equal to 10% by weight, and more particularly less than or equal to 5% by weight, relative to the total weight of said electrode.
• the electrode may be free of electronic conductive additive.
• the electrode may further comprise one or more binder (s).
• Such binders can be chosen from fluorinated binders, in particular from polytetrafluoroethylene, polyvinylidene fluoride, polysaccharides or latices, in particular of the styrene-butadiene rubber (SBR or styrene-butadiene rubber) type.
• the said binder (s) may be present in an amount of less than or equal to 50% by weight, relative to the total weight of the electrode, preferably less than or equal to 20% by weight, in particular less than or equal to 10% by weight, and more particularly less than or equal to 5% by weight, relative to the total weight of the electrode.
• an electrode according to the invention may comprise less than 10% by weight of fluorinated binders, in particular less than 5% by weight of fluorinated binders, relative to the total weight of the electrode.
• an electrode according to the invention is free of binder.
• An electrode may further comprise other additives commonly used for secondary lithium battery electrodes.
• An electrode according to the invention can be prepared according to different techniques.
• the electrode according to the invention may be formed by a process for preparing an electrode as defined above, comprising at least the steps consisting in:
• step (ii) depositing said mixture of step (i) by coating or by a printing technique on a base substrate.
• the dispersion of step (i), when it is aqueous, can also comprise a thickener, for example of carboxymethylcellulose, hydroxypropyl methylcellulose type, and / or a surfactant and / or a salt (LiOH for example).
• a dispersion is also commonly called "ink”.
• the ink may for example be deposited according to step (ii) on a current collector, such as a metal sheet, for example aluminum.
• the deposition of the ink can for example be carried out by flexography, heli-engraving, screen printing, inkjet or spray. The skilled person is able to adjust the conditions of implementation of these different techniques.
• the base substrate may be a polymeric film of polyethylene or polypropylene type, the step (ii) of the deposition of the ink then being followed by a subsequent step (iii) of taking off said polymeric film , to form a self-supporting electrode.
• the electrode may be formed by electropolymerization in situ in solution.
• a layer formed of polymers according to the invention may be more particularly formed by electropolymerization of the monomers functionalized directly on a current collector, such as, for example, a sheet of aluminum, nickel, copper, steel or carbon. , where appropriate in the presence of additional electronic conductors.
• the invention thus relates, in another of its aspects, to a method for preparing an electrode as defined above, comprising the formation of said polymer by electropolymerization in situ on a current collector, of monomers carrying at least one group having at least one nitroxide function, said monomers being selected from the family of fluorenes, carbazoles, anilines, phenylenes, isothionaphthenes, acetylenes, phenylenevinylenes and mixtures thereof.
• electropolymerization takes place directly within a lithium electrochemical cell.
• electropolymerization takes place during the first charge cycle (or discharge) of the cell and the electrode is formed in situ on the collector of the positive (or negative) electrode respectively.
• the method of forming the electrode by in situ electropolymerization may comprise at least the steps of:
• the electrolyte solution may be chosen from the electrolytes conventionally used for lithium batteries, through which the Li + cations have the possibility of migrating.
• the electrolyte may, for example, consist of a salt comprising at least the Li + cation.
• the salt is, for example, selected from L1CIO 4, LiAsF 6, L1PF 4 L1BF 4 LiRpSC, L1CH3SO3, Li (RFS02) 2, LIN (RFS0 2) 3; RF being selected from a fluorine atom and a perfluoroalkyl group having from 1 to 8 carbon atoms.
• the salt is preferably dissolved in an aprotic polar solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate, ethylmethyl carbonate; and it can be supported by a separator element disposed between the first and second electrodes, the separator element being soaked with electrolyte.
• an aprotic polar solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate, ethylmethyl carbonate
• solubilization of the active material according to the invention in a solvent optionally in the presence of additional electronic conductors, and deposition of the solution by a conventional technique, for example chosen from the techniques printing (flexography, heli-engraving, screen printing, inkjet, spray ...), drop casting, dip-coating, spinning.
• a conventional technique for example chosen from the techniques printing (flexography, heli-engraving, screen printing, inkjet, spray ...), drop casting, dip-coating, spinning.
• Implementation in solution facilitates the deposition on soft collectors of the polymer type with a metal deposit or carbonaceous fabrics; or
• the extrudate will be in the form of a rod which will be applied to the current collector by compression (isostatic press, calendering, etc.) or preferably in the form of a film which will be deposited in the molten state. directly on a collector electrical conductor (Al, Ni, Cu, steel, carbon ).
• an electrode formed from the electrode material according to the invention is particularly advantageous with regard to its use in lithium secondary batteries.
• the present invention relates to a lithium secondary battery comprising an electrode according to the invention.
• It can be a lithium-ion, lithium-polymer, lithium-sulfur, lithium-air or supercapacitor battery.
• an electrode according to the invention is implemented in a lithium-ion battery.
• the lithium-ion batteries have an architecture with two electrodes (a positive electrode and a negative electrode), both coated on an electrically conductive current collector, arranged on either side of an organic separator or inorganic.
• the two mounting techniques of this architecture currently the most used are the winding (winding of the various constituents in a cylindrical or prismatic geometry) and the stack (stack layer by layer of the different elements).
• winding winding of the various constituents in a cylindrical or prismatic geometry
• stack stack layer by layer of the different elements.
• other mounting techniques to form a battery are possible, such as printing techniques.
• the electrode according to the invention can constitute the positive electrode or the negative electrode of the battery. Preferably, it will constitute the positive electrode.
• Example 1 Infrared spectrum of TEMPO-mesylate (formed according to Example 1c), polyfluorene and TEMPO grafted polyflurorene formed according to Example 3;
• FIG. 2 cyclic voltammetric of the TEMPO grafted polyfluorene.
• the hydroxy-TEMPO is introduced into a flask under an argon atmosphere and dissolved in dichloromethane. 1 equivalent of base (triethylamine) and thionyl chloride are introduced dropwise. This mixture is stirred at 45 ° C for 24 hours. The solution is then washed with water and then with brine and finally dried over magnesium sulfate. After filtration, the solvent is evaporated under vacuum.
• the hydroxy-TEMPO is introduced into a flask under an argon atmosphere and dissolved in dichloromethane.
• 1.1 equivalents of base (triethylamine) are added to the reaction medium at 0 ° C. and then 1 equivalent of methane chloride or toulenesulfonyl is introduced dropwise. This mixture is stirred at 25 ° C for 24 hours.
• the solution is then washed with water, with an aqueous solution of sodium hydrogencarbonate and finally with brine and then dried over magnesium sulfate. After filtration, the solvent is evaporated under vacuum.
• Fluorene or 2,7-dibromofluorene is introduced into a flask under an argon atmosphere and dissolved in THF. 4 basic equivalents (K 2 CO 3 or NaH) are introduced. 1 equivalent of functionalized TEMPO (TEMPO mesylate or halogeno-TEMPO) is then dissolved in THF and this solution is added dropwise to the reaction medium. The mixture is introduced into water, extracted with ether and then dried over magnesium sulfate. The product is then dried under vacuum.
• the fluorene or fluorene grafted TEMPO is introduced into a flask under an argon atmosphere and dissolved in chloroform.
• the iron (III) chloride (5 equivalents) dissolved in nitromethane is then added dropwise to the reaction medium at -78 ° C. This mixture is stirred at 25 ° C. for 70 hours and then introduced dropwise into methanol with vigorous stirring. Hydrazine (10 equivalents) and ethylenediaminetetraacetic acid (10 equivalents) are added to the solution and the reaction mixture is stirred for 24 hours.
• the suspension is then filtered and washed with water and methanol.
• a Soxhlet extraction is then performed with acetone and the product is dissolved in 100 mL of chloroform and dried over magnesium sulfate. The solvent is then evaporated under vacuum.
• the 2,7-dibromo fluorene or 2,7-dibromofluorene grafted TEMPO is introduced into a flask under an argon atmosphere and dissolved in DMF.
• the zinc powder (4 equivalents) and the Ni (COD) 2 (10 mol%) are then added to the reaction medium at -78 ° C.
• This mixture is stirred at 25 ° C. for 70 hours and then filtered and washed with methanol in the presence of ethylenediaminetetraacetic acid (10 equivalents).
• the suspension is then filtered and then washed with methanol, with hydrochloric acid and finally with water.
• the powder obtained is dissolved in chloroform, dried over magnesium sulfate and then precipitated in methanol, filtered and dried under vacuum.
• the polyfluorene is introduced into a flask under an argon atmosphere and dissolved in THF. Sodium hydride (4 equivalents) is then added and this mixture is stirred at 25 ° C for 2 hours. 1 equivalent of functionalized TEMPO (TEMPO mesylate or halogen-TEMPO) is then dissolved in THF and this solution is added dropwise to the reaction medium and stirred for 24 hours. The mixture is introduced into water, extracted with ether and washed with brine and then dried over magnesium sulfate. The product is then dried under vacuum and reprecipitated in methanol.
• TEMPO TEMPO mesylate or halogen-TEMPO
• the TEMPO grafted polyfluorene is introduced into 2 ml of a 1 mol / l solution of lithium hexafluorophosphate in a mixture of ethylene carbonate, propylene and dimethyl carbonate in volume proportion. 1/1/3. 5 sweeps at a speed of 1 mV / s between 2.5 and 4.7 V are performed.
• a lithium-metal battery of the "button cell” type is produced with: a lithium negative electrode in the form of a disc 16 mm in diameter and 130 ⁇ in thickness and deposited on a stainless steel disk serving as a current collector;
• a positive electrode consisting of a disk 14 mm in diameter taken from a composite film 50 ⁇ m thick comprising the composite material of the invention prepared according to example 1 deposited on an aluminum current collector (sheet of 20 microns thick);

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