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    • 专利摘要:
    The present invention relates to a high energy density Lithium Metal Polymer (LMP) battery comprising as a positive electrode active material a high potential compound and as a solid polymer electrolyte an AB or BAB type block copolymer. , A being an ethylene oxide block and B being an anionic polymer block based on lithium bis (trifluoromethylsulfonyl) imide.
    公开号:FR3049114A1
    申请号:FR1652306
    申请日:2016-03-18
    公开日:2017-09-22
    发明作者:Renaud Bouchet；Marc Deschamps
    申请人:Institut Polytechnique de Grenoble；Blue Solutions SA；
    IPC主号:
    专利说明:

    The present invention relates to a high energy density Lithium Metal Polymer (LMP) battery comprising as a positive electrode active material a high potential compound and as a solid polymer electrolyte an AB or BAB type block copolymer. , A being an ethylene oxide block and B being an anionic polymer block based on lithium bis (trifluoromethylsulfonyl) imide.
    It applies in particular to the field of electric and hybrid vehicles, in which there is a growing demand for autonomous systems and high energy density, while ensuring a low environmental impact.
    The Lithium Metal Polymer batteries currently on the market are in the form of a thin film wound several times or several thin films stacked. This wound or stacked thin film has a thickness of the order of a hundred micrometers and comprises: a negative electrode (anode) ensuring the supply of lithium ions during the discharge; a positive electrode (cathode) acting as a receptacle where the lithium ions are interposed; a solid polymer electrolyte conducting lithium ions and located between the positive electrode and the negative electrode; and a current collector connected to the positive electrode to provide the electrical connection. The negative electrode is generally made of a sheet of lithium metal or a lithium alloy; the solid polymer electrolyte is generally composed of a polymer based on poly (ethylene oxide) (POE) and at least one lithium salt; the positive electrode is usually a material whose working potential is less than 3.8V vs Li + / Li (ie the insertion / deinsertion potential of lithium is less than 3.8V vs Li + / Li) such as for example LiFePO4 ; and the current collector is generally made of a sheet of metal. The conductivity of the ions is ensured by the dissolution of the lithium salt in the poly (ethylene oxide). The high molecular weight POE doped with lithium salt has very good mechanical properties at room temperature, but is also a semi-crystalline polymer. The crystal structure restricts the mobility of the chains and decreases the ionic conductivity of the polymer. Above the POE melting temperature (Tf ~ 60-65 ° C), the ionic conductivity increases considerably, but at these temperatures the POE becomes a viscous liquid and loses its dimensional stability. Thus, although POE is a very good ionic conductor, easy to formulate, it does not have sufficient mechanical strength at the temperatures usually used in an LMP battery (60-80 ° C). Other polymers based on poly (ethylene oxide) (POE) have been described, such as random copolymers of the poly (ethylene oxide-propylene oxide) type (ie POE-stat-PPO), block copolymers of polystyrene-b-POE type (ie PS-b-POE), crosslinked POE or copolymers comprising acrylate or methacrylate chains to which POE is connected. Furthermore, it is known to add POE-based polymer inorganic or organic particles, possibly nanometric, such as particles of aluminum oxide, titanium oxide or cellulose nanofibres. However, these optionally composite polymer materials replacing the POE in the solid polymer electrolyte are mainly intended to enhance the mechanical properties of the solid polymer electrolyte and / or to break the crystallinity of the POE in order to obtain a better conductivity at low temperature and / or or a barrier to dendritic growth and do not improve the energy density of the battery.
    Moreover, in the aforementioned solid polymer electrolytes, the lithium salt is dissolved in a POE polymer matrix and the Li + charge fraction (also called cationic transport number) is low (<20%), due to the fact that strong interaction between lithium cation and POE chains, which limits electrical performance. The value of the cation transport number determines the portion of current carried by the cation. A low cationic transport number results in the formation of a salt concentration gradient in the thickness of the electrolyte during operation of the battery. This behavior generates a salt depletion at the electrode, inducing an increase in the resistance of the electrolyte and reduced power performance, and promotes the formation of lithium dendrites, causing a fall in faradic efficiency and in the long term, short -Circuits.
    In order to remedy this problem, the international application WO 2013/034848 describes AB type diblock copolymers or BAB type triblocks, in which block A is an unsubstituted polyoxyethylene chain having a number average molecular weight. less than or equal to 100 kDa and block B is an anionic polymer capable of being prepared from one or more monomers chosen from vinyl monomers and derivatives, said monomers being substituted by the anion of a sulfonyl salt ( lithium trifluoromethylsulfonyl) imide (TFSILi) of formula (I) below:
    wherein * represents the point of attachment of the anion of said salt of formula (I) to said monomer via a covalent bond or a linear alkyl chain having from 1 to 5 carbon atoms.
    International application WO 2013/034848 also describes a lithium metal polymer battery comprising the following components: a negative electrode made of lithium metal, a solid polymer electrolyte consisting of one of the above-mentioned BAB triblock copolymers [e.g. PSTFSILi-b-PEO-b-PSTFSILi containing 30.8% by weight of PSTFSILi, relative to the total weight of the copolymer], and a positive electrode consisting of 60% by weight of LiFePO 4, 8% by mass of carbon black and 32% by weight of said triblock copolymer. However, the energy density of such a battery is not optimized (e.g. density of about 515 Wh / kg relative to the mass of active material). On the other hand, AB type diblock copolymers or POE type BAB type triblock copolymers, although having a transport number equal to 1, have a lower ionic conductivity than POE alone.
    In parallel, the research was directed towards the modification of the positive electrode active material in an LMP battery comprising as a solid polymer electrolyte a polymer based on POE and a lithium salt. However, full LMP battery tests are quite infrequent and are essentially limited to the use of low potential active materials vs Li + / Li (i.e. with a potential below 3.8V). Indeed, POE-based polymer materials generally decompose / oxidize above 3,8V vs. Li + / Li, resulting in irreversible degradation of battery performance. Therefore, when a positive electrode active material of potential greater than or equal to 3.8V vs Li + / Li is used, such as LiFexMni-xPO4 in which 0 <x <1 (potential of 4.25V vs Li + / Li at the end of charging), a rapid drop in capacity is observed as demonstrated in Comparative Example 2 of the present application and as described below. Therefore, it is not yet possible to take advantage of active materials operating at a higher potential than that of LiFePO4 (potential of 3.43V vs. Li + / Li), since solid polymer electrolytes based on POE are known to induce a limited life of the system.
    Therefore, no prior art describes both the modification of the active material and the solid polymer electrolyte, in order to improve the performance of a LMP battery in terms of energy density, while guaranteeing good resistance. cycling.
    Thus, the object of the present invention is to overcome the drawbacks of the aforementioned prior art and to provide a lithium metal polymer battery with high energy density while guaranteeing good stability to cycling (ie able to operate on a large number of of cycles).
    The object of the invention is achieved by the LMP battery which will be described below.
    The inventors of the present application have in fact surprisingly discovered that it was possible to combine, within an LMP battery, a positive electrode material of high insertion / de-insertion potential of the Li + ions with a polymer electrolyte. POE-based solid which does not decompose or oxidize in the electrochemical window of use of the cell, said positive electrode material having a surface chemistry compatible with the solid polymer electrolyte based on POE.
    The subject of the present invention is therefore an LMP (lithium metal polymer) battery comprising: at least one negative electrode comprising lithium metal or a lithium metal alloy; at least one positive electrode comprising at least one active substance whose potential is greater than 3.8 V vs Li + / Li, and preferably greater than or equal to 4V, at least one block copolymer Pi and at least one agent generating an electronic conductivity, said positive electrode possibly being supported by a current collector, and at least one solid polymer electrolyte comprising at least one block copolymer Pi, said lithium metal polymer battery being characterized in that: the active material of the positive electrode is chosen from: (1) olivine-type active materials chosen from those of formula UFexMni-xP04 in which 0 <x <0.4, those of formula LiMgyMni.yP04 in which 0 <y <0.2 and those of formula LiTtTT'i-tP04 in where 0 <t <1 and T and T 'are different and are selected from Fe, Mn, Co, Ni and Ti, (2) fluorophosphate active materials such as UVPO4F, and (3) active ingredients of the type. lamellar oxide LiM02 with M representing a mixture of at least two metals chosen from Al, Ni, Mn and Co, such as LiNii / 3MnI / 3Coi / 302 (family of NMCs), LiNi0.8Co0.15AI0.05O2 (family of N CA) or LiNiO, 5MnO, 502, and the block copolymer Pi is an AB type diblock copolymer or BAB type triblock in which the block A is an unsubstituted polyoxyethylene chain having a number average molecular weight. less than or equal to approximately 100 kDa; and block B is an anionic polymer capable of being prepared from one or more vinyl monomers substituted with the anion of a lithium sulfonyl (trifluoromethylsulfonyl) imide salt (TFSILi) of formula (I) below:
    in which * represents the point of attachment of said anion of formula (I) to said vinyl monomer via a covalent bond, of a linear alkyl chain, optionally perfluorinated, having 1 to 5 carbon atoms or a linear alkoxy chain, optionally perfluorinated, having from 1 to 5 carbon atoms, and preferably via a covalent bond.
    In the present invention, the term "linear alkoxy chain having 1 to 5 carbon atoms" means a linear alkyl chain having 1 to 5 carbon atoms and further comprising one or more oxygen atoms in said alkyl chain.
    In the LMP battery of the invention, the selected positive electrode materials are capable of withstanding high voltages (greater than 3.8V vs. Li + / Li) and the selected solid polymer electrolytes do not decompose in the electrochemical window of use of the cell and are compatible with the selected active ingredients. On the other hand, the block copolymer Pi has a cation transport number close to unity, which makes it possible to reduce the polarization to the electrodes during the fast charging and discharging steps and thus to obtain a greater power density, while avoiding the germination of dendrites. Moreover, the LMP battery of the invention makes it possible to carry out numerous cycles at fairly drastic speeds with a charging terminal at 4.3V vs. Li + / Li, without the capacity collapsing. The battery of the invention is therefore a good compromise to ensure good resistance to cycling and good performance in power and energy density.
    The block copolymer Pi has a phase nanoseparation with domains mainly composed of POE and domains predominantly composed of PVTFSILi (PV means vinyl polymer, that is to say polymer obtained from vinyl monomers). The presence of the particular lithium salt TFSILi improves the stability of the block copolymer Pi, especially at high voltages vs Li + / Li. The POE phase has ion transport properties within the battery and the PVTFSILi polar phase is preferentially located on the positive electrode side to form a stable and non-reactive nanoscale interfacial layer between the positive electrode active material and the phase POE. Thanks to this layer, the POE phase, which brings the ionic conduction within the solid polymer electrolyte, does not feel the deleterious effects related to the potential on the surface of the electrode.
    In the block copolymers Pi according to the invention, the anion of the salt of formula (I) is attached to the chain constituting block B, either directly via a covalent bond or via an alkyl or alkoxy chain, optionally perfluorinated. The only mobile ion after dissociation of the copolymer is the Li + cation, which confers on it specific properties (good conductivity, cation transport number Li + (t +) close to 1) while also having good mechanical strength.
    According to the invention, the block A preferably comprises from 225 to 2250 ethylene oxide units, and even more preferably from 500 to 1150 ethylene oxide units. A most preferred value is 795 ethylene oxide units.
    The average molecular weight of the block A is always less than or equal to about 100 kDa, and preferably varies from about 10 to 60 kDa and even more preferably from 15 to about 50 kDa.
    As the polyoxyethylene chain is unsubstituted, this means that the POE within the copolymer is linear. Such a configuration makes it possible to guarantee good mechanical strength of the electrolyte and of the composite electrode.
    The vinyl monomers substituted with the anion of a lithium sulfonyl (trifluoromethylsulfonyl) imide salt (TFSILi) of formula (I) may be vinyl aromatic or nonaromatic monomers. By way of example of vinyl aromatic monomers, mention may be made of lithium sulfonyl (trifluoromethylsulfonyl) imide styrene and its derivatives, especially derivatives in which the phenyl group of styrene is substituted by one or more groups chosen from methyl groups, ethyl, tert-butyl, a bromine atom and a chlorine atom.
    Lithium sulfonyl (trifluoromethylsulfonyl) imide styrene is preferred and may be represented by the following formula (ΙΙ-a):
    By way of example of non-aromatic vinyl monomers, mention may be made of lithium sulfonyl (trifluoromethylsulfonyl) imide, lithium sulfonyl (trifluoromethylsulfonyl) imide, lithium sulfonyl (trifluoromethylsulfonyl) imide, and the like. lithium sulfonyl (trifluoromethylsulfonyl) imidide methacrylamide, lithium ethylene sulfonyl (trifluoromethylsulfonyl) imide, lithium propylene sulfonyl (trifluoromethylsulfonyl) imide, lithium dienesulfonyl (trifluoromethylsulfonyl) imide and maleimide-sulfonyl (trifluoromethylsulfonyl) imide of lithium.
    The sulfonyl methacrylate (trifluoromethylsulfonyl) lithium imide is preferred and may be represented by the following formula (ΙΙ-b):
    Block B preferably results solely from the polymerization of one or more vinyl monomers substituted with the anion of a lithium sulfonyl (trifluoromethylsulfonyl) imide salt (TFSILi) of formula (I) as defined in the invention.
    The aromatic vinyl monomers are preferred.
    According to a preferred embodiment of the invention, the block copolymer Pi is chosen from P-type (STFSILi) -b-POE-b-P tri-block copolymers (STFSILi).
    Particularly preferred copolymers according to the present invention are the copolymers P (STFSILi) -b-POE-bP (STFSILi), in which each of the blocks PSTFSILi has a number average molecular weight ranging from 2000 to 7500 g / mol and the block central POE a number average molecular weight of about 35000 g / mol.
    A still more particularly preferred copolymer according to the present invention is the copolymer P (STFSILi) -b-POE-bP (STFSILi), in which each of the blocks PSTFSILi has a number average molecular weight of about 4900 g / mol and the central POE block a number average molecular weight of about 35000 g / mol.
    The P (STFSILi) -b-POE-bP copolymers (STFSILi) used in the present invention can have a P (STFSILi) / POE ratio varying from approximately 10 to 80% by weight, preferably ranging from 46 to 73% by weight. about, and more preferably about 50 to 70% by weight.
    The Pi block copolymers can be prepared by any controlled polymerization method (ATRP ("Atom Transfer Radical Polymerization"), RAFT ("reversible addition fragmentation chain transfer"), anionic, cationic, NMP ("Nitroxide-Mediated Radical Polymerization"). or directly by using a vinyl monomer as defined in the invention bearing the anion of a potassium sulphonyl (trifluoromethylsulfonyl) imide salt (TFSIK) of formula (Γ) below:
    wherein * represents the point of attachment of said anion of formula (Γ) to said monomer via a covalent bond, a linear, optionally perfluorinated, alkyl chain having 1 to 5 carbon atoms or a linear alkoxy chain, optionally perfluorinated, having from 1 to 5 carbon atoms, and preferably via a covalent bond, - or indirectly by implementing a vinyl monomer as defined in the invention (ie unsubstituted by the anion of a sulfonyl salt (trifluoromethylsulfonyl) potassium imide), then by post-functionalization of the polymer obtained [ie by grafting the anion of the salt of formula (Γ)].
    Said polymerization (or post-functionalization when it exists) can then be followed by an ion exchange step so as to replace the K + cation with a Li + cation. By way of example, when the synthesis is carried out according to the NMP method, it consists in synthesizing at first a POE-based macroalkoxyamine and then in copolymerizing said macroalkoxyamine and the vinyl monomers carrying an anion of formula (Γ) such defined in the invention, then to perform an ion exchange so as to replace the cation K + by a cation Li +. The synthesis of POE-based macroalkoxyamines can be carried out according to the method described in international application WO 2007/113236. The synthesis of the vinyl monomers carrying the anion of formula (Γ) as defined in the invention may for example be carried out according to the method described by R. Meziane et al. [Electrochimica Acta, 2011, 57, 14-19].
    More specifically, it comprises at least the following steps: i) the copolymerization of the vinyl monomers bearing the anion of formula (Γ) as defined in the invention with a macroalkoxyamine of formula (III) below:
    ** being the point of attachment of the SGI patterns at one end of the POE pattern when η = 1 and at each end of the POE pattern when n = 2, POE being a poly (ethylene oxide) chain having a number average molecular weight of less than about 100 kDa; then ii) the exchange of K + cations by Li + cations.
    Thus, according to this process, the reaction of a macroalkoxyamine of formula (III) in which η = 1 leads to the production of an AB type di-block copolymer and the use of a macroalkoxyamine of formula (III) in which n = 2, leads to the production of a triblock copolymer of BAB type.
    The first step is preferably carried out in a polar solvent such as for example Ν, Ν-dimethylformamide (DMF), dimethylsulfoxide (DMSO) or water, at a temperature ranging from 80 to 120 ° C., for a period of time. from 2 to 20 hours approximately. The exchange of the cations of step ii) can for example be carried out using a dialysis membrane, using a lithium salt such as for example lithium chloride.
    When step ii) is complete, the resulting copolymer is then preferably washed to remove the excess lithium salt and possibly the excess vinyl monomer which has not polymerized, then the solution is preferably evaporated under vacuum to allow the storage of the copolymer. The solid polymer electrolyte does not preferably comprise lithium salts other than those of formula (I) as defined in the invention which are grafted to the B blocks via their anions. The solid polymer electrolyte preferably does not include plasticizers and / or solvents, such as those conventionally used in gelled polymeric electrolytes or in liquid electrolytes (e.g. carbonates).
    According to a particularly preferred embodiment of the invention, the solid polymer electrolyte consists of one or more block copolymers Pi as defined in the invention. The solid polymer electrolyte may in particular be in any suitable form, for example in the form of a sheet, a film or a membrane. The solid polymer electrolyte may be prepared by any technique known to those skilled in the art such as for example by coating, extrusion or pressing (cold or hot). The agent generating an electronic conductivity may be chosen from carbon black, SP carbon, acetylene black, carbon fibers and nanofibers, carbon nanotubes, graphene, graphite, metal particles and fibers and one of their mixtures. The agent generating an electronic conductivity may represent from 0.1 to 10% by weight approximately, and preferably from 0.1 to 2% by weight approximately, relative to the total mass of the positive electrode. The positive electrode further comprises at least one block copolymer Pi as defined in the invention, which makes it possible to prevent the formation of a concentration gradient in the thickness of the positive electrode during the cycling and thus of to improve the power performance of the battery or to increase the grammage of the cathode. This also ensures stable interfaces with the active ingredient of high potential.
    The block copolymer Pi as defined in the invention may represent from 15 to 35% by weight, preferably from 18 to 28% by weight approximately, relative to the total mass of the positive electrode.
    The block copolymer Pi of the positive electrode may be identical to or different from the block copolymer Pi of the solid polymer electrolyte of the battery. They are preferably identical.
    According to a preferred embodiment of the invention, the basis weight of the positive electrode (ie the amount of positive electrode active material / cm 2 / area) is greater than or equal to about 0.2 mAh / cm 2. and preferably, it varies from 0.5 to 3.5 mAh / cm 2 approximately.
    The current collector may be a stainless steel or aluminum current collector, optionally covered with a carbon-based layer (anticorrosive layer).
    The active material of the positive electrode may represent about 60 to 85% by weight, and preferably about 65 to 80% by weight, relative to the total weight of the positive electrode.
    The active material of the positive electrode is a lithium intercalation material. It has a surface chemistry compatible with the block copolymer Pi as defined in the invention.
    The active material of the positive electrode is preferably an active ingredient (1) of olivine type as defined in the invention, and more preferably an active material of formula LiFexMni-xPO4 in which 0 <x <0.4, and preferably wherein x = 0.2.
    The active material of the positive electrode is a reversible active material of lithium ions. In other words, it can reversibly insert or disintegrate lithium ions.
    The ideal operating temperature of the battery of the invention is about 60 to 100 ° C.
    The present invention is illustrated by the following exemplary embodiments, to which it is however not limited.
    EXAMPLES
    Raw materials used in the examples: oxalyl chloride, anhydrous acetonitrile (Alfa-Aesar), sodium salt of 4-styrene sulfonic acid, dimethylformamide (DMF), triethylamine, dimethylaminopyridine (DMAP), lithium chloride, dichloromethane, acryloyl chloride, diethyl ether, tetrahydrofuran (THF) (Sigma-Aldrich), trifluoromethylsulfonamide (Rhodia), -Nitroxide of formula (SGI) (Arkema):
    Poe a, hydroxylated co (Mn = 10,000 g / mol) (Sigma-Aldrich), MAMA-SG1 of the following formula (Arkema):
    - carbon black C65 (Timcal), - stainless steel current collector (Goodfellow), - lithium metal sheet (Blue Solutions).
    EXAMPLE 1 Preparation of a Lithium Metal Polymer Battery According to the Invention 1) Synthesis of a Triblock Copolymer PSTFSIL1-d-PEO-d-PSTFSILi Comprising 28% by Weight of PSTFSILI 1.1) Synthesis of 4-styrene Potassium sulfonyltrifluoromethylsulfonylimidide (FSTFSIK) 1.1.1) Synthesis of 4-sulfonyl-styrene chloride 2 ml of oxalyl chloride (23.3 mmol) and 0.087 g (1 mmol) of dimethylformamide (DMF) were added in 40 ml. anhydrous acetonitrile. The reaction medium was stirred for 5 hours to promote the formation of a Vilsmeier-Haack complex (complex between DMF and oxalyl chloride (CH3) 2N + = CCIH). After the solution had turned yellow, 4 g of 4-styrene sulfonic acid sodium salt was slowly added to the reaction mixture under nitrogen and at room temperature. The reaction mixture was then stirred for 24 hours at room temperature. The above amount of NaCl formed was removed by filtration. 42 ml of 4-sulfonyl-styrene chloride solution was obtained. 1 H NMR (300 MHz, DMSO-d 6, 298 K): δ ppm 7.59 (d, 2H); 7.44 (d, 2H); 6.72 (q, 1H); 5.84 (d, 1H); 5.27 (d, 1H); 5.27 (d, 1H). 13 C NMR (75 MHz, DMSO-d6, 298 K): δ ppm 146.91; 137.66; 136.16; 125.93; 125.72; 115.18. 1.1.2) Synthesis of potassium 4-stvenene-sulfonyltrifluoromethylsulfoniumimide (fSTFSIK) 8.1 ml of triethylamine (28.2 mmol), 2.89 g of trifluoromethylsulfonamide (19.4 mmol) and a catalytic amount of DMAP (about 215 mg) ) were added successively in 30 ml of anhydrous acetonitrile. The reaction mixture was stirred for 1 hour. The 4-sulfonyl-styrene chloride solution obtained above in step 1.1.1) was cooled to 0 ° C., and the reaction medium containing trifluoromethylsulfonamide was slowly added thereto. The resulting mixture was stirred vigorously for 16 hours. After evaporation of the solvent, a brown solid was recovered which was then dissolved in 50 ml of dichloromethane. This solution was washed twice with 20 ml of a 4% aqueous solution of NaHCO 3 and then with 20 ml of 1M hydrochloric acid. Potassium 4-styrene-sulfonyl (trifluoromethylsulfonyl) imide was obtained by neutralizing the acidic monomer with excess K 2 CO 3 in water. The resulting suspension was stirred for 1 hour, filtered and dried to give 4.2 g of the expected product as a light yellow solid. Recrystallization from water gave 3.63 g of powder (yield about 53%). 1 H NMR (300 MHz, DMSO-d 6, 298 K): δ ppm 7.73 (d, 2H); 7.57 (d, 2H); 6.79 (q, 1H); 5.95 (d, 1H); 5.38 (d, 1H). 13 C NMR (75 MHz, DMSO-d6, 298 K): δ ppm 144.21; 139.55; 135.57; 126.43; 125.87; 126.36. 1.2) Synthesis of macroalcoxvamine PEO-diSGl
    Macroalkoxyamine SG1-MAMA-POE-MAMA-SG1 (or PEO-diSG1) was synthesized of the following formula:
    wherein SGI is as defined in the invention and the value of p is such that the number average molar mass (i.e. Mn) of the POE is 35,000 g / mol.
    To do this, 10 g of ΡΟΕ-α, ω hydroxylated (Mn = 10,000 g / mol) and 1.4 ml of triethylamine were solubilized in a three-necked flask containing 40 ml of dichloromethane. The reaction mixture was degassed by bubbling nitrogen for 20 minutes. Using a dropping funnel, 0.9 ml of solubilized acryloyl chloride (5 eq) in 10 ml of dichloromethane was then added dropwise at a temperature of 90 ° C. It was allowed to react for about 15 hours. The reaction mixture was filtered to remove triethylammonium chloride. The filtrate was washed twice with 20 ml of saturated aqueous NaHCO 3 solution. The organic phase was precipitated in diethyl ether. POE diacrylate was recovered by filtration and then dried under vacuum. Then 2 g of POE diacrylate was introduced into a "Schlenk" equipped with a "Rotaflo". 0.16 g (4.2 mmol) of MAMA-SG1 of formula indicated above, dissolved in 6 ml of THF, were introduced on the POE diacrylate. The suspension was deoxygenated by sparging with nitrogen for 30 minutes. The "Schlenk" was immersed in an oil bath thermostated at 100 ° C for 1 hour. THF was evaporated in vacuo at room temperature.
    The expected PEO-diSG1 was obtained. 1.3 Synthesis of a Block Copolymer of PSTFSILi-b-PEO-b-PSTFSILi at 28% by Weight of PSTFSILi 2.5 g of Macroalkoxyamine PEO-DiSG1 obtained above in the previous step 1.2) (ie 6, 9 × 10 -5 mol), 1.2 g of STFSIK (ie 3.4 × 10 -3 mol) obtained above in step 1.1), 2.5 × 10 -3 g of nitroxide of formula SGI ( purity at 85% by weight 7.2 x 10'6 mole), and 3.5 ml of DMF were placed in a three-necked flask equipped with a condenser, a bubbler and a magnetic bar. The mixture was degassed for 20 minutes by bubbling argon to remove oxygen from the reaction medium. The mixture was then heated at 110 ° C for 4 h. The polymerization reaction was stopped by immersing the flask in an ice bath. The solvent (DMF) was then evaporated under vacuum and the resulting residue was dissolved in 30 ml of deionized water. The solution obtained was then placed in a dialysis membrane sold under the trade name Cellu-Sep® T2 by the company Orange Scientific, having a retention threshold (MWCO) of 6,000-8,000 Da and dialysed with 4 times 1 liter of lithium chloride solution (0.25 mol / l), in order to carry out the K + cation exchange with the Li + cations (0.25 mol / l), then with 4 times 1 liter of deionized water in order to remove excess lithium chloride. The dialysis step also eliminated the monomer and the remaining DMF. The copolymer solution was then evaporated under vacuum.
    The expected block copolymer in which each of the blocks PSTFSILi had a number-average molecular weight of 6800 g / mol (estimated from 28% by mass measured by NMR) was obtained by coating and the POE central block a mean molecular mass. in number of 35000 g / mol, the PSTFSILi block representing 28% by weight of the total mass of the copolymer.
    Pi block copolymer PSTFSILi-POE-PSTFSILi as obtained by coating was in the form of a film of about 70 μιτι thickness. 2) Preparation of a positive electrode
    A positive electrode in the form of a film was prepared as follows: A mixture of 0.5 g of UFe0.4Mn0.6PO4 and 0.065 g of carbon black was manually ground in cyclohexane for 20 minutes. After drying the resulting mixture, the resulting powder was poured into a solution of Pi block copolymer PSTFSILi-POE-PSTFSILi as prepared in step 1) above dissolved at 10% by mass in a 50/50 solution by volume dichloromethane / acetonitrile and corresponding to a block copolymer mass Pi of 0.242 g.
    The resulting mixture was stirred magnetically for 2 hours and then degassed a few seconds under vacuum before being coated on a stainless steel current collector using the method Dr. Blade well known to those skilled in the art. After evaporation of the solvents, the electrode obtained in the form of a film was dried at 60 ° C for 2 hours and then at room temperature under vacuum for 24 hours and finally stored in a glove box. The positive electrode obtained comprised 62% by weight of active material, 30% by weight of block copolymer Pi and 8% by weight of carbon black. It had a thickness of about 12 μm. The grammage obtained was 0.25 mAh / cm 2.
    3) Preparation of an LMP battery
    An LMP battery was prepared by assembling in a glove box: a block copolymer film Pi PSTFSILi-POE-PSTFSILi as prepared in step 1) with a thickness of 70 μm, a sheet of lithium metal approximately 60 μm thick, and a positive electrode approximately 12 μm thick as prepared in stage 2). The assembly was then rolled at 3.4 bar and 80 ° C to form a battery. The battery was then sealed in a coffee bag to be tested outside the glove compartment.
    Cycling tests were conducted at 80 ° C. in a Memmert chamber at 80 ° C. (± 0.2 ° C.) using a Biologie VMP3 potentiostat. The cycling conditions were galvanostatic at C / 15, D / 10 or D / 7. The charging terminals were 4.2 or 4.3V vs. Li + / Li and 2.8V vs LiVLi.
    The appended FIG. 1 shows the voltage (in volts, V) as a function of C / C ° (where C is the capacity restored during cycling in mAh and C ° being the total capacity expected in mAh) at 80 ° C of the battery. according to the invention as prepared in Example 1 (curve with the solid line) and for comparison at 25 ° C of a battery not according to the invention (curve with the dotted lines).
    The battery not in accordance with the invention comprised a lithium metal foil as a negative electrode, a Celgard separator impregnated with a solution containing 1 LiPF 6 in a mixture of ethylene carbonate / dimethyl carbonate (1/1 by weight) as a liquid electrolyte, and a mixture of 80% by weight of UFe0.4Mno, 6PO4, 10% by weight of C65 carbon black and 10% by weight of PVdF, as a positive electrode.
    Less polarization is observed and trays much better defined at the discharge with the battery of the invention.
    Thus, the use of a solid electrolyte such as that of the invention instead of a liquid electrolyte ensures good electrochemical performance, or better, while ensuring a good mechanical strength within the battery and avoid all safety issues related to the use of a liquid electrolyte.
    The appended FIG. 2 shows the capacitance (in mAh / g) restored as a function of the number of cycles of the battery of the invention during charging (curve with full diamonds) and during discharge (curve with solid squares). The curve with the solid triangles shows the faradic efficiency (in%) as a function of the number of cycles of the battery of the invention.
    The inventors have found that the tests when they are repeated several times are reproducible for at least 60 cycles.
    Furthermore, the low-speed cycling conditions used make it possible to obtain capacities restored close to 1 and are particularly drastic with respect to the electrochemical stability since at each cycle (C / 15, D / 10) the solid polymer electrolyte is at a potential higher than 4.1V vs. Li + / Li for more than 15 hours. This means that after about 30 cycles, the solid polymer electrolyte can remain more than 450 hours at high potential and this at a particularly high temperature of 80 ° C. With cycling at (C / 4, D / 2), the number of cycles required to achieve the same high potential residence time (ie, 450 hours) would be more than 180 cycles.
    Comparative Example 2 Preparation of a Lithium Metal Polymer Battery Not in Accordance with the Invention
    FIG. 3 shows the capacity (in mAh / g) as a function of the number of cycles of a battery not in accordance with the invention during charging.
    The battery which does not conform to the invention comprises: a lithium metal sheet as negative electrode; a solid polymer electrolyte containing 47.6% by weight of poly (ethylene oxide-butylene co-oxide) (co- P (EO) - (OB), ICPSEB, 115,000 g / mol, Nippon shokubai), 12.4% by weight of LiTFSI, and 40% by weight of PVDF-HFP copolymer (21510, Solvay), and - positive electrode containing 74% by weight of UFe0.4Mn0.6PO4 as prepared in Example 1, 0.5% by weight of Ketjenblack carbon black (EC600-jd, AkzoNobel), 20.1% by weight of P (EO) - (OB) (ICPSEB, 115,000 g / mol, Nippon shokubai) and 5.4% by weight of LiTFSI.
    Figure 3 shows a rapid drop in capacity.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    A lithium metal polymer battery comprising: at least one negative electrode comprising lithium metal or a lithium metal alloy; at least one positive electrode comprising at least one active substance whose potential is greater than 3.8 V vs Li + / Li, at least one block copolymer Pi and at least one agent generating an electronic conductivity, said positive electrode possibly being supported by a current collector, and - at least one solid polymer electrolyte comprising at least one block copolymer Pi, said lithium metal battery polymer being characterized in that: the active material of the positive electrode is chosen from: (1) olivine-type active materials chosen from those of formula LiFexMni-xPO4 in which 0 <x <0.4, those of formula UMgyMni-yP04 in which 0 <y <0.2 and those of formula LiTtT'i.tP04 in which 0 <t <1 and T and T 'are different and are chosen from Fe, Mn, Co, Ni and Ti, ( 2) fluorophosphate active materials, and (3) lamellar oxide active materials with M representing a mixture of at least two metals selected from Al, Ni, Mn and Co, and the block copolymer Pi is a AB type diblock copolymer or BAB triblock copolymer in which block A is an unsubstituted polyoxyethylene chain having a number average molecular weight less than or equal to 100 kDa; and block B is an anionic polymer capable of being prepared from one or more vinyl monomers substituted with the anion of a lithium sulfonyl (trifluoromethylsulfonyl) imide salt (TFSILi) of formula (I) below:

    wherein * represents the point of attachment of said anion of formula (I) to said vinyl monomer via a covalent bond, a linear alkyl chain having 1 to 5 carbon atoms or a linear alkoxy chain having 1 to 5 carbon atoms.
    [2" id="c-fr-0002]
    2. Battery according to claim 1, characterized in that the block A comprises from 225 to 2250 ethylene oxide units.
    [3" id="c-fr-0003]
    3. Battery according to claim 1 or 2, characterized in that the average molecular weight of the block A varies from 10 to 60 kDa.
    [4" id="c-fr-0004]
    4. Battery according to any one of the preceding claims, characterized in that the vinyl monomers are aromatic vinyl monomers selected from styrene sulfonyl (trifluoromethylsulfonyl) imide lithium and its derivatives.
    [5" id="c-fr-0005]
    5. Battery according to any one of the preceding claims, characterized in that the block copolymer Pi is chosen from P type (STFSILi) -b-POE-b-P tri-block copolymers (STFSILi).
    [6" id="c-fr-0006]
    6. Battery according to claim 5, characterized in that the ratio P (STFSILi) / POE varies from 50 to 70% by weight.
    [7" id="c-fr-0007]
    7. Battery according to any one of claims 1 to 3, characterized in that the vinyl monomers are non-aromatic vinyl monomers selected from lithium sulfonyl (trifluoromethylsulfonyl) imide acrylate, sulfonyl methacrylate (trifluoromethylsulfonyl) imide of Lithium, lithium sulfonyl (trifluoromethylsulfonyl) imide, lithium sulfonyl (trifluoromethylsulfonyl) imide, lithium ethylene-sulfonyl (trifluoromethylsulfonyl) imide, lithium propylene sulfonyl (trifluoromethylsulfonyl) imide, and the like. lithium dienes-sulfonyl (trifluoromethylsulfonyl) imide and lithium maleimide-sulfonyl (trifluoromethylsulfonyl) imide.
    [8" id="c-fr-0008]
    8. Battery according to any one of the preceding claims, characterized in that the solid polymer electrolyte does not comprise lithium salts other than those of formula (I) as defined in claim 1 which are grafted to the blocks B by through their anions.
    [9" id="c-fr-0009]
    9. Battery according to any one of the preceding claims, characterized in that the solid polymer electrolyte does not include plasticizers and / or solvents.
    [10" id="c-fr-0010]
    10. Battery according to any one of the preceding claims, characterized in that the agent generating an electronic conductivity is selected from carbon black, SP carbon, acetylene black, carbon fibers and nanofibers, nanotubes. carbon, graphene, graphite, metal particles and fibers and one of their mixtures.
    [11" id="c-fr-0011]
    11. Battery according to any one of the preceding claims, characterized in that the agent generating an electronic conductivity represents from 0.1 to 10% by weight, relative to the total mass of the positive electrode.
    [12" id="c-fr-0012]
    12. Battery according to any one of the preceding claims, characterized in that the block copolymer Pi represents from 15 to 35% by weight, relative to the total mass of the positive electrode.
    [13" id="c-fr-0013]
    13. Battery according to any one of the preceding claims, characterized in that the active material of the positive electrode is 60 to 85% by weight, relative to the total mass of the positive electrode.
    [14" id="c-fr-0014]
    14. Battery according to any one of the preceding claims, characterized in that the active material of the positive electrode is an active material of formula LiFexMni.xPO4 in which 0 <x <0.4.
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    同族专利:
    公开号 | 公开日
    CA3018099A1|2017-09-21|
    EP3430660B1|2020-06-17|
    WO2017158310A1|2017-09-21|
    FR3049114B1|2018-03-09|
    US11050083B2|2021-06-29|
    JP2019513283A|2019-05-23|
    KR20180126532A|2018-11-27|
    EP3430660A1|2019-01-23|
    SG11201807620SA|2018-10-30|
    KR102160592B1|2020-09-28|
    US20190088997A1|2019-03-21|
    CN109075338A|2018-12-21|
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    CN112920354A|2021-01-28|2021-06-08|远景动力技术有限公司|Block polymers and lithiation and methods of making and using the same|
    法律状态:
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    2017-09-22| PLSC| Publication of the preliminary search report|Effective date: 20170922 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1652306A|FR3049114B1|2016-03-18|2016-03-18|POLYMER LITHIUM METAL BATTERY WITH HIGH ENERGY DENSITY|
    FR1652306|2016-03-18|FR1652306A| FR3049114B1|2016-03-18|2016-03-18|POLYMER LITHIUM METAL BATTERY WITH HIGH ENERGY DENSITY|
    JP2018548410A| JP7034930B2|2016-03-18|2017-03-17|High energy density metal lithium polymer battery|
    EP17714877.2A| EP3430660B1|2016-03-18|2017-03-17|Lithium metal polymer battery having a high energy density|
    CA3018099A| CA3018099A1|2016-03-18|2017-03-17|Lithium metal polymer battery having a high energy density|
    SG11201807620SA| SG11201807620SA|2016-03-18|2017-03-17|Lithium metal polymer battery having a high energy density|
    CN201780018337.7A| CN109075338A|2016-03-18|2017-03-17|High-energy density lithium metal-containing polymer battery|
    US16/085,345| US11050083B2|2016-03-18|2017-03-17|Lithium metal polymer battery having a high energy density|
    KR1020187030128A| KR102160592B1|2016-03-18|2017-03-17|High energy density lithium metal polymer battery|
    PCT/FR2017/050630| WO2017158310A1|2016-03-18|2017-03-17|Lithium metal polymer battery having a high energy density|
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