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  • 专利说明
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    • 专利摘要:
    The present invention relates to a composite material comprising sulfur and carbon, a positive electrode comprising such a composite material as an active material and its manufacturing method, a lithium-sulfur battery comprising such a positive electrode and its method of manufacture.
    公开号:FR3018516A1
    申请号:FR1452087
    申请日:2014-03-13
    公开日:2015-09-18
    发明作者:Margaud Lecuyer；Marc Deschamps；Joel Gaubicher；Bernard Lestriez；Dominique Guyomard
    申请人:Centre National de la Recherche Scientifique CNRS；Universite de Nantes；Blue Solutions SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of lithium-sulfur batteries with high energy and power densities. In particular, the present invention relates to a composite material comprising sulfur and carbon, a positive electrode comprising such a composite material as active material and its manufacturing method, a lithium-sulfur battery comprising such a positive electrode and its method of manufacture. manufacturing. Lithium batteries have become indispensable components in many devices that include portable devices, such as mobile phones, computers and light equipment, or heavier devices such as two-wheeled vehicles (bicycles). , mopeds) or four-wheeled vehicles (electric or hybrid motor vehicles). They are also widely studied for use in the field of stationary energy storage. A lithium battery comprises at least one negative electrode and at least one positive electrode between which is placed a solid electrolyte or a separator impregnated with a liquid electrolyte. For example, the liquid electrolyte consists of a lithium salt dissolved in a solvent chosen to optimize the transport and dissociation of the ions. The positive electrode is constituted by a current collector supporting an electrode material which contains at least one positive electrode active material capable of reversibly inserting lithium ions; the negative electrode is constituted by a sheet of lithium metal (possibly supported by a current collector), a lithium alloy or a lithium intermetallic compound (lithium battery), or by a current collector supporting a electrode material which contains at least one negative electrode active material capable of reversibly inserting lithium ions (lithium ion: Li-ion battery). Each electrode material generally further comprises a polymer which acts as a binder (e.g. polyvinylidene fluoride or PVdF) and / or an electronic conductivity conferring agent (e.g., carbon).
    [0002] During the operation of the battery, lithium ions pass from one to the other of the electrodes through the electrolyte. During discharge of the battery, an amount of lithium reacts with the positive electrode active material from the electrolyte, and an equivalent amount is introduced into the electrolyte from the active material of the negative electrode, the lithium concentration thus remaining constant in the electrolyte. The insertion of the lithium into the positive electrode is compensated by supplying electrons from the negative electrode via an external circuit. During charging, the reverse phenomena take place.
    [0003] The various components of a lithium battery are chosen so as to produce at the lowest possible cost batteries that have a high energy density, good cycling stability and operate safely. One of the most promising electrochemical energy storage systems is the lithium-sulfur battery on the one hand because the elemental sulfur S8 is an inexpensive element, and on the other hand, because such a battery can reach theoretically a specific capacity and a high energy mass density respectively of 1675 mAh / gsoufre and 2600 Wh / kg ', f', if elemental sulfur S8 is completely reduced to lithium sulphide Li2S at a voltage close to 2 volts (per relative to the torque Li ± / Li °). By comparison, the mass densities of energy currently obtained are 200-250 Wh / kg for the best Li-ion batteries, 100-150 Wh / kg for a Na-ion battery, 500 Wh / kg for a lithium battery -air and 50 Wh / kg for a redox flow battery (well known under the anglicism "redox-flow battery"). Such a lithium-sulfur battery generally comprises a negative electrode (ie anode) made of lithium metal or a lithium-based alloy, a positive electrode (ie cathode) comprising sulfur or an organic compound comprising sulfur as a material active, and an electrolyte comprising a lithium salt. Sulfur and sulfur-containing organic compounds, however, have the disadvantage of being electrically and ionically insulating (e.g. S8 electron conductivity = 5 x 10-30 S.cm-1 at 25 ° C). In order to allow a reversible electrochemical reaction at high current regimes, the sulfur must therefore be in intimate contact with an electrically conductive additive such as carbon. Thus, Lécuyer et al. [Journal of Power Sources, 2013, 241, 249] have described a method of preparing a positive electrode comprising sulfur and carbon, said method comprising a step of mixing at 80 ° C a carbon black (Ketjenblack® ), a lithium salt (LiClO 3 .3H 2 O), a copolymer of poly (ethylene oxide) (POE), optionally PVdF, and sulfur in water or propylene carbonate in order to obtain an electrode paste; then a step of rolling at 95 ° C of said electrode paste on an aluminum current collector covered with a carbon-based layer, to obtain a positive electrode in the form of a film; and finally a drying step at 105 ° C of said electrode to evaporate the remaining water. Lecuyer et al. also disclose a lithium-sulfur battery comprising said positive electrode, a lithium foil as a negative electrode, and a solid polymer electrolyte based on POE. However, the tests carried out with said battery show that during the discharge, the sulfur is transformed into long-chain polysulfides which are soluble and, as a result, diffuse into the polymer electrolyte. This diffusion causes significant changes in the volume of the swelling polymer electrolyte and the positive electrode which loses its initial morphology. This leads to the collapse of said positive electrode after a few cycles and to a poor cyclability of the battery. Zhao et al. [Solid State Ionics, 2012, 234, 40] have described a pretreatment of the carbon and sulfur mixture prior to the preparation of the positive electrode to improve its electronic conductivity and to prevent dissolution of the polysulfides in the electrolyte. This pretreatment comprises a step of mixing a mesoporous carbon black with sulfur in tetrahydrofuran, then a step of grinding in a ball mill of the mixture of the preceding step, then a drying step under vacuum at 60 ° C. for 6 hours in order to evaporate the tetrahydrofuran, then a first heat treatment step under argon at 150 ° C for 5 hours to allow incorporation of the molten sulfur into the pores of the carbon black, and finally a second treatment step Heat under argon at 300 ° C for 3 hours to evaporate the remaining sulfur and form a carbon / sulfur composite as the electrode active material. This pretreatment, however, has the disadvantages on the one hand, not to be used at the industrial stage since it has many steps and uses sophisticated and relatively expensive equipment; and on the other hand, not to allow the introduction of a large amount of sulfur in the carbon / sulfur composite formed. Indeed, the high temperatures used during the second heat treatment favor the incorporation of sulfur (vapor phase) in the micropores of carbon black and all the sulfur which was on the surface of the mesopores after the first heat treatment s evaporates. Moreover, the two heat treatments are performed in a tubular furnace under argon, that is to say in an unclosed environment, thus promoting the vaporization of sulfur. Moreover, the cathode obtained from said carbon / sulfur composite comprises only 43% by weight of sulfur relative to the total mass of the electrode. However, during assembly of the battery, the electrolyte "fill" said electrode, inducing a decrease in the mass proportion of sulfur in the electrode thus filled before cycling. However, it is necessary to introduce and keep in the positive electrode a large amount of sulfur to achieve a high energy density of the battery. The object of the present invention is to overcome the disadvantages of the aforementioned prior art and to provide a composite material comprising sulfur and carbon in which the sulfur is present in large quantities and is dispersed homogeneously, said composite material being economical preparing and improving the electrochemical performance of a lithium-sulfur battery when used as a positive electrode active material. In addition, another object of the present invention is to develop an economical battery in which the diffusion of the polysulfides in the electrolyte and the collapse of the positive electrode are avoided, thus ensuring the obtaining of a better cyclability.
    [0004] These objects are achieved by the invention which will be described below. The invention therefore has for its first object a composite material comprising sulfur (S) and carbon (C), characterized in that it is obtained according to the following steps: i) a step of mixing an essentially mesoporous carbonaceous agent and a sulfur-containing agent, the amount of sulfur (S) in said mixture ranging from about 75% to about 85% by weight, ii) a step of grinding the mixture obtained in the preceding step i), iii) a step of heat treatment of the crushed mixture obtained in the preceding step ii) in a closed container, at a temperature sufficient to melt the sulfur, iv) a grinding step of the heat-treated mixture of the preceding step iii), and in that said carbonaceous agent used in step i) has the following characteristics: an SBET specific surface greater than or equal to 700 m2 / g, and preferably greater than or equal to 800 m2 / g, said specific surface being calculated by the m B.E.T. method (i.e. Brunauer method, Emmett and Teller, 1938), - average mesopore size of about 4 to 10 nm, said size being calculated by the B.J.H method (i.e. method of Barrett, Joyner and Halenda, 1951), a total pore volume greater than or equal to about 1 cm 3 / g, and preferably greater than or equal to about 1.5 cm 3 / g, said total pore volume being calculated by BET method, said sulfur agent being selected from elemental sulfur S8 and an organic sulfur compound comprising at least one SS bond. In the present invention, the term "substantially mesoporous carbonaceous material" means that the carbonaceous material comprises a mesoporous volume of at least about 70% by volume of the total pore volume, preferably at least about 80% by volume of the pore volume. total, and more preferably at least about 90% by volume of the total pore volume, said mesoporous volume being calculated from the BJH method. In the present invention, the expression "carbonaceous agent" means an agent essentially comprising carbon, that is to say comprising at least about 80% by weight of carbon, preferably at least about 90% by weight of carbon, and more preferably at least about 95% by weight of carbon. In the description which follows and unless explicitly stated otherwise, all the specific surface area values indicated were calculated by the B.E.T. method. Similarly, all indicated mesopore size values were calculated by B.J.H. Finally, all the total pore volume values indicated were determined by the B.E.T method and all the mesoporous volume values were calculated by the B.J.H. method. The carbonaceous agent is preferably carbon black. As an example of carbon black having the characteristics defined above, mention may be made of the carbon blacks marketed under the references: Ketjenblack 600JD®, Ketjenblack 700JD® and Timcal 20 Ensaco 350G®. The specific surface area of the carbonaceous agent is preferably greater than or equal to about 1000 m 2 / g, and still more preferably greater than or equal to about 1400 m 2 / g. According to a preferred embodiment of the invention, the total pore volume of the carbonaceous agent is greater than or equal to about 2 cm3 / g, and preferably greater than or equal to about 2.5 cm3 / g. Preferably, the carbonaceous particles are in the form of spherical particles (ie in the form of beads) in order to promote the conduction, in particular in the direction perpendicular to the positive electrode (ie in the direction of its thickness), and thus to facilitate the electrochemical exchanges between the positive electrode and the negative electrode. In fact, the carbonaceous particles in the form of spherical particles have a propensity to form three-dimensional conductive networks. When the carbonaceous particles are in the form of spherical particles, this means that several carbon atoms form spheres. Thus, in order to promote conduction in the transverse direction of the positive electrode (ie in the direction of its thickness), the carbonaceous agent is preferably not in the form of fibers or platelets such as carbon fibers or graphene platelets, since these will move preferentially in the direction of manufacture of the film. In a particularly preferred embodiment of the invention, the carbonaceous agent comprises spherical carbon particles having a mean diameter ranging from about 20 nm to about 100 nm. Thus, each sphere comprising a plurality of carbon atoms has a mean diameter ranging from about 20 nm to about 100 nm. In a preferred embodiment, the amount of sulfur (S) in the mixture of step i) ranges from about 80% to about 85% by weight. The particle size of the sulfur agent used in step 1) is not critical. Thus, any size of sulfur-containing particles may be used. The sulfur-containing organic compound may be chosen from organic polysulfides, in particular those of the general formula R 1 -S-Sn-R 2 in which R 1 and R 2, which may be identical or different, represent a linear, substituted or cyclic alkyl chain, which may comprise from 1 to to 20 carbon atoms, and n being from 1 to 50; and disulfide polymers having a sequence of S-S bonds that can be broken during the discharge cycle of a lithium-sulfur battery, and reformed during the charge cycle. Step ii) grinding facilitates the homogeneous distribution of sulfur on the carbon. It can be carried out manually, in particular by means of a mortar or mechanically, in particular by means of a ball mill. The sufficient temperature of step iii) is advantageously chosen so that the sulfur is in the liquid state, and the viscosity of the molten sulfur is low.
    [0005] The sufficient temperature of the heat treatment of step iii) may range from about 115 ° C to about 270 ° C, preferably from about 130 ° C to about 220 ° C, and more preferably from about 140 ° C to about 170 ° C. The duration of the heat treatment of step iii) can range from about 30 minutes to 24 hours, and preferably from 1 to about 5 hours. Step iii) is preferably carried out under a dry air atmosphere, in particular having a dew point less than or equal to -30 ° C. The inventors of the present application have thus discovered that when the carbonaceous agent has a particular mesopore size of 4 and 10 nm, the sulfur is capable, during step iii), of filling the porosity of the agent. carbon. Indeed, the pore size of the carbonaceous agent must be sufficiently high (that is to say greater than 4 nm) to allow the molten sulfur to penetrate inside the pores, but sufficiently low (this is less than 10 nm) to exert sufficient retention of polysulfides during cycling. In addition, the high specific surface (SBET 700 m 2 / g) of the carbonaceous agent makes it possible to obtain a thin layer of sulfur over the entire skeleton formed by the carbonaceous agent and to avoid the formation of agglomerates of sulfur in the composite material of the invention and thereby the rapid diffusion of sulfur during cycling. The large pore volume is also necessary to effectively retain polysulfides formed during cycling. Finally, the composite material of the invention has a thin homogeneously distributed sulfur coating, thus increasing its accessibility during electrochemical reactions and its mechanical stability. Stage iv) can be carried out manually, in particular using a mortar or mechanically, in particular using a ball mill. Thus, at the end of step iv), the composite material comprising sulfur and carbon according to the invention is structured so that the sulfur forms a surface coating of the carbonaceous agent by entering the mesopores of it.
    [0006] The method may further comprise between step iii) and step iv), a cooling step of the closed container comprising the ground mixture. According to a preferred embodiment, the process for obtaining the composite material of the invention does not include any other heat treatment step (s) than step iii). The method for conducting the composite material of the invention is simple, fast, and does not require a complex device. With this process, the coating of the carbonaceous agent with sulfur is facilitated with a low production cost. The second object of the invention is a positive electrode characterized in that it comprises: at least one composite material comprising sulfur and carbon and as defined in the first subject of the invention, as an active ingredient of electrode, at least one polymeric binder P1, at least one linear low molecular weight polyether, and at least one lithium salt L1, and in which the sulfur (S) represents at least about 40% by weight. preferably at least about 45% by weight, and more preferably at least about 50% by weight, based on the total weight of said positive electrode. In the present invention, "linear low molecular weight polyether" means a linear polyether of molar mass less than or equal to about 20,000 g-mol-1, preferably less than or equal to about 2000 g-mol-1, and more preferably less than or equal to about 600 g-mol-1. In the present invention, "a low molecular weight liquid linear polyether" is also referred to as "polyether". It should be noted that the total mass of the positive electrode 30 comprises the mass of the composite material, the mass of the polymeric binder, the mass of the polyether and the mass of the lithium salt L1.
    [0007] The positive electrode may comprise from about 2 to about 20 weight percent polyether, and preferably about 8 to about 18 weight percent polyether, based on the total weight of the positive electrode. The polyether may be chosen from: polyethylene glycols of the formula H- [O-CH 2 -CH 2] m-OH in which m is between 1 and 13, the glycol ethers of formula R- [O-CH 2 -CH 2] In which p is between 1 and 13 and R and R ', which may be identical or different, are linear, substituted or cyclic alkyl groups, which may comprise from 1 to 20 carbon atoms; formula R1- [CH2-0], 1-R1 'in which q is between 1 and 13, R1 and R1', which are identical or different, are linear, substituted or cyclic alkyls, which may comprise from 1 to 20 carbon atoms and optionally heteroatoms, cyclic ethers, cyclic polyethers, and a mixture thereof. The polyether (s) used in the positive electrode of the invention are particularly stable vis-à-vis lithium and sulfur compounds, thus limiting the maximum parasitic reactions. In a preferred embodiment, the polyether is tetraethylene glycol dimethyl ether (TEGDME) of the formula CH 3 O- (CH 2 -CH 2) 4-OCH 3 (i.e. R, R '= CH 3 and p = 4). According to a particular embodiment, the positive electrode comprises from 5 to 20% by weight of polymer binder P1, and preferably from 5 to 15% by weight of polymer binder P1, relative to the total mass of the polymer. positive electrode. The polymer binder P1 may be chosen from ethylene and propylene copolymers, or a mixture of at least two of these polymers; homopolymers and copolymers of ethylene oxide (e.g. POE, POE copolymer), methylene oxide, propylene oxide, epichlorohydrin or allyl glycidyl ether, or mixtures thereof; halogenated polymers such as homopolymers and copolymers of vinyl chloride, vinylidene fluoride (PVdF), vinylidene chloride, ethylene tetrafluoride, or chlorotrifluoroethylene, copolymers of vinylidene fluoride and hexafluoropropylene (PVdF). co-HFP) or mixtures thereof; polyacrylates such as polymethyl methacrylate; polyalcohols such as polyvinyl alcohol, electron-conducting polymers such as polyaniline, polypyrrole, polyfluorenes, polypyrenes, polyazulenes, polynaphthalenes, polyacetylenes, poly (p-phenylenevinylene), polycarbazoles, polyindoles, polyazepines, polythiophenes, p-phenylene polysulfide or mixtures thereof; cationic type polymers such as polyethyleneimine (PEI), polyaniline in the form of emeraldine salt (ES), poly (N-vinylimidazole quaternized) or mixtures thereof; and one of their mixtures.
    [0008] A cationic type polymer (i.e. positively charged) makes it possible to improve the retention of the polysulfides which are negatively charged in the positive electrode, and thus to limit the diffusion of the polysulphides in the electrolyte during the cycling. The polymeric binder P1 is preferably PEI or ES.
    [0009] According to a preferred embodiment of the invention, the positive electrode comprises only PE1 or ES as polymer binder P1. In a particular embodiment, the positive electrode of the invention does not include an agent conferring electronic conductivity other than the carbonaceous agent of the composite material as defined in the first subject of the invention. Indeed, the presence of the carbonaceous agent in the composite material of the invention can suffice to give the positive electrode sufficient electronic conductivity to allow proper operation of the battery. The positive electrode may comprise from about 2 to about 25% by weight of lithium salt L1, preferably from about 3 to about 15% by weight of lithium salt L1, and more preferably from about 3 to about 8% by weight of lithium salt. lithium salt L1, relative to the total mass of the positive electrode. The lithium salt L1 may be chosen from lithium fluoride (LiFO3), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium fluoroborate (LiBF4), lithium metaborate (LiBO2), lithium perchlorate (LiCIO4) and lithium nitrate (LiNO3), lithium bis (fluorosulfonyl) imide (LiFSI), and mixtures thereof. LiTFSI is the preferred lithium salt.
    [0010] The positive electrode of the invention may have a porosity less than or equal to about 40% by volume, and preferably less than or equal to about 30% by volume, relative to the total volume of the electrode. This makes it possible to improve the energy density of the battery. The third object of the invention is a method of manufacturing a positive electrode as defined in the second subject of the invention, characterized in that it comprises the following steps: a) a step of mixing a material composition comprising sulfur and carbon and as defined in the first subject of the invention with at least one polymeric binder P1, at least one lithium salt L1, at least one low molecular weight liquid linear polyether, and optionally at least one at least one solvent of said polymer binder P1, to obtain an electrode paste, b) a step of applying said electrode paste to at least one support, c) a step of drying said electrode paste to obtain an electrode paste, 25 positive electrode in the form of a supported film. The polymeric binder P1, the lithium salt L1, and the low molecular weight liquid linear polyether are as defined in the second subject of the invention. Step a) may be carried out by extrusion or grinding. Extrusion is very advantageous since it makes it possible to easily obtain low porous electrodes while using little solvent. It also makes it possible to avoid a calendering step on the dry electrode which can cause changes in the structure of the electrode, adversely affect the good coating of the grains of the carbonaceous agent, and thus can induce a collapse of the electrode at the electrode. course of cycling. Finally, the calendering step has the disadvantage of increasing the number of steps to obtain the electrode, and thus its cost of production. The solvent of the polymer binder P1 of step a) makes it possible to solubilize said polymeric binder P1. When present, said solvent is preferably less than about 30% by weight of the total mass of the blend of composite material, polymeric binder P1, lithium salt, and polyether. The use during manufacture of the positive electrode of a small amount of solvent of the polymeric binder P1, leads to a positive electrode of low porosity (i.e. 40% by volume approximately). This low porosity makes it possible to control and optimize the amount of sulfur present in the positive electrode, and thus to achieve optimum energy density densities. The solvent of step a) may be selected from water, N-methylpyrrolidone, carbonate type solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate or methyl and ethyl carbonate, acetone, alcohols such as methanol, ethanol or propanol, and mixtures thereof. Step b) can be carried out by rolling or coating. The support may be a current collector and / or a support film. As an example of a current collector, there may be mentioned an aluminum current collector covered with a carbon-based layer (anticorrosive layer). As an example of a support film, there may be mentioned a plastic film 30 of polyethylene terephthalate (PET) silicone type.
    [0011] The supported positive electrode film obtained at the end of step c) may have a thickness ranging from about 2 to 100 amps, and preferably from 10 to 60 pm. Step c) can be performed at a temperature sufficient to remove the solvent from step a). The fourth subject of the invention is a lithium-sulfur battery, characterized in that it comprises: a positive electrode as defined in the second subject of the invention or as manufactured in the third subject of the invention; a metal negative electrode chosen from lithium and a lithium alloy; a gelled polymer electrolyte comprising at least one low molecular weight liquid linear polyether, at least one lithium salt L2, and at least one polymeric binder P2. The gelled polymer electrolyte may comprise from 20 to 45% by weight of L 2 lithium salt, and preferably from 30 to 45% by weight of L 2 lithium salt relative to the total weight of the gelled polymer electrolyte. . The lithium salt L2 may be chosen from lithium fluoride (LiFO3), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium fluoroborate (LiBF4), metaborate of lithium lithium (LiBO2), lithium perchlorate (LiCIO4), lithium nitrate (LiNO3), lithium bis (fluorosulfonyl) imide (LiFSI), and mixtures thereof. LiTFSI is the preferred lithium salt. The gelled polymer electrolyte may comprise from about 3 to about 20% by weight of polyether, and preferably from about 3 to about 10% by weight of polyether, based on the total weight of the gelled polymer electrolyte. The linear low molecular weight polyether (i.e. polyether) is as defined in the second subject of the invention.
    [0012] The polyether (s) used in the electrolyte of the battery of the invention are particularly stable vis-à-vis lithium and sulfur compounds, thus allowing to minimize the parasitic reactions.
    [0013] In a preferred embodiment, the polyether is TEGDME. The polymeric binder P2 can be chosen from polyolefins such as homopolymers or copolymers of ethylene and propylene, or a mixture of at least two of these polymers; homopolymers and copolymers of ethylene oxide (e.g. POE, POE copolymer), methylene oxide, propylene oxide, epichlorohydrin or allylglycidyl ether, or mixtures thereof; halogenated polymers such as homopolymers and copolymers of vinyl chloride, vinylidene fluoride (PVdF), vinylidene chloride, ethylene tetrafluoride, or chlorotrifluoroethylene, copolymers of vinylidene fluoride and hexafluoropropylene (PVdF). co-HFP) or mixtures thereof; anionic-type non-conductive electronic polymers such as poly (styrene sulfonate), poly (acrylic acid), poly (glutamate), alginate, pectin, or mixtures thereof; polyacrylates; and one of their mixtures.
    [0014] The gelled polymer electrolyte may comprise from 40 to 80% by weight of polymer binder P2, and preferably from 50 to 60% by weight of polymer binder P2, relative to the total weight of the gelled polymer electrolyte. The inventors of the present application have discovered that the battery of the invention, although comprising a large amount of sulfur in the positive electrode (ie at least 50% by weight of sulfur), does not see its capacity decrease from the first cycles by comparison with the batteries of the prior art, indicating that the disconnection of the grains of active material is avoided during cycling.
    [0015] The gelled polymer electrolyte used slows the diffusion of the polysulfides and thus stabilizes the capacity of the battery by limiting the parasitic reactions. Since the polyether of the electrolyte is in liquid form, it makes it possible to solubilize a larger quantity of lithium salt than with a solid polymeric polyether. The large presence of salt in the electrolyte slows the diffusion of polysulfides therein. When the battery is in operation, a lower amount of active material therefore leaves the positive electrode through the use of such a gelled polymer electrolyte. It will also be appreciated that the gelled polymer electrolyte allows lithium ions to more readily reach sulfur in the porosity of the carbonaceous agent relative to a dry (i.e. solid) polymer electrolyte. Finally, compared to a separator impregnated with liquid electrolyte, the gelled polymer electrolyte of the invention has a better resistance to dendrites and has the advantage of being self-supporting. The battery according to the invention can operate between about 20 and 110 ° C, and preferably between 60 and 100 ° C. Due to the gelled nature of the electrolyte, it is also possible to slightly lower the operating temperature of the battery compared to a solid electrolyte battery (LMP), which can further improve the cyclability of the battery. battery. The fifth subject of the invention is a method for manufacturing a lithium-sulfur battery as defined in the fourth subject of the invention, characterized in that it comprises the following steps: A) a preparation step of a gelled polymer electrolyte as defined in the fourth subject of the invention, in particular by mixing at least one linear low molecular weight liquid polyether, at least one lithium salt L2 and at least one polymer binder P2, and then extruding the mixing to obtain an electrolyte paste and then rolling the electrolyte paste between two support films; and B) a step of assembling a positive electrode as defined in the second subject of the invention or as manufactured according to the method as defined in the third subject of the invention, of a negative electrode, and gelled polymer electrolyte as obtained in the previous step A).
    [0016] The low molecular weight liquid linear polyether, the lithium salt L2 and the polymeric binder P2 are as defined in the fourth subject of the invention. The two support films can be silicone PET plastic films. The present invention is illustrated by the following examples, to which it is however not limited. EXAMPLES The raw materials used in the examples are listed below: - carbon black "porous carbon" (BET surface area: 2000 m 2 / g), ACS Material - carbon black "Specialty carbon black 5303", Asbury - carbon black "ENSACOTM 350G Conductive Carbon Black", 15 Timcal - carbon black "Ketjenblack 600JD®", AkzoNobel - sulfur S8, 99.5% purity, Sigma Aldrich - POE copolymer, "ZSN 8100", Zeospan - copolymer of poly (vinylidenedifluoride and hexafluoropropylene) (PVdF-co-HFP), Solvay, polyethylene imine (PEI), 50% (w / v) in H2O, Sigma Aldrich-polyaniline in salt form Emeraldine (ES) , Sigma Aldrich - LiTFSI, 3M, 25 - Silicone PET Film, Mitsubishi Unless otherwise indicated, all materials were used as received from manufacturers.
    [0017] EXAMPLE 1 Preparation of Several Composite Materials A, B, 1 and 2 Four carbon / sulfur mixtures were prepared by mixing each of the ACS, Asbury, Timcal and Ketjenblack carbon blacks with S8 sulfur in the following mass proportions C / S: 21 , 7 / 78.3 (with carbon blacks ACS, Timcal and Ketjenblack) and 18.8 / 81.2 (with Asbury carbon black). The four C / S blends thus obtained were then ground in a mortar and stored in four closed containers.
    [0018] The four containers each containing one of the various milled carbon and sulfur mixtures were subjected to a heat treatment at a temperature of 155 ° C for 2 hours. The heat treated mixtures were then grinded to obtain the following four composite materials: - A comprising ACS, - B carbon black comprising Asbury carbon black, - 1 comprising Timcal carbon black and - 2 comprising black Ketjenblack carbon. Table 1 below shows the characteristics [specific surface area (in m2 / g), total pore volume (in cm3 / g), pore volume (in cm3 / g), average pore diameter (in nm)] of the different blacks of carbon used to prepare the corresponding composite materials A, B, 1 and 2: TABLE 1 Carbon Black ACS Asbury Timcal Ketjenblack Specific Surface 3802 183 860 (BET) 1529 (BET) (m2 / g) (Langmuir) (BET) Volume total 1.34 0.49 1.21 3.24 (cm3 / g) (<283 nm) a (<277 nm) a (<192 nm) a (<126 nm) a Volume ND 0.30 0.96 2.84 BJH (cm3 / g) 2-50 nm Average Diameter 2.17 10.62 5.63 8.48 Pore (BET) (nm) Average Diameter ND 7.89 4.93 7.74 Pore (BJH) (nm) Composite material A (*) B (*) 1 2 obtained (*): Composite materials not forming part of the invention (a): maximum average pore diameter taken into account to calculate the total volume.
    [0019] The various carbon blacks tested in the various composite materials do not have the same characteristics (pore size, pore volume, porous surface, etc ...) and therefore have very different performances. It should be noted that the composite materials 1 and 2 are in accordance with the invention, while the composite materials A and B do not form part of the invention since the carbon blacks ACS and Asbury from which the composite materials A and B were respectively obtained do not have the desired characteristics in terms of porous structure. The specific surface area, the total pore volume, the BJH pore volume, the average pore diameter of each of the carbon blacks ACS, Asbury, Timcal and Ketjenblack were evaluated using an apparatus sold under the trade name ASAP2010. , by the company Micromeritics.
    [0020] Figures 1, 2, 3 and 4 respectively show composite materials A, B, 1 and 2 by scanning electron microscopy (SEM). Figures lb, 2b, 3b and 4b are respectively magnifications of a portion of Figures la, 2a, 3a and 4a.
    [0021] The scanning electron microscopy (SEM) analysis was carried out using an apparatus sold under the trade name JSM-7600F by the company Jeol. Figure 1 shows that the composite material A not forming part of the invention and prepared from carbon black ACS, comprises agglomerates of sulfur. Indeed, the carbon black ACS has an average pore size too small to allow sulfur to be incorporated and dispersed homogeneously in the carbon black ACS. The presence of large agglomerates of sulfur causes the collapse of the positive electrode during cycling and does not achieve good cycling. As indicated in the present invention, the pore size of the carbon must be sufficiently high (i.e. greater than 4 nm) to allow the molten sulfur to penetrate the pores, but sufficiently low (e.g. that is, less than 10 nm) to exert sufficient retention of polysulfides during cycling. FIG. 2 shows that in the composite material B not forming part of the invention and prepared from Asbury carbon black, the sulfur seems better dispersed locally even if it is not present on the entire surface of the black of Asbury carbon. Indeed, the Asbury carbon black has an average pore size of the order of 9-10 nm, however the specific surface of the Asbury carbon black is not sufficient to allow the sulfur to be well distributed in the porosity carbon. Finally, its total pore volume is also not high enough that all the sulfur can be contained inside it. Figures 3 and 4 show that composite materials 1 and 2, forming part of the invention and prepared respectively from Timcal and Ketjenblack carbon blacks have the same structure as the base carbon blacks. A gloss indicates the presence of sulfur. The sulfur, after this pretreatment, is distributed homogeneously around the carbon grains and does not form agglomerates on the outside thereof. By way of comparison, FIG. 5 shows a mixture of Ketjenblack carbon black and elemental sulfur (mass proportions: 18.8% Ketjenblack carbon black and 81.2% elemental sulfur) per SEM after step ii) of grinding and before step iii) heat treatment. It is observed that the sulfur does not coat the carbon grains and is not dispersed homogeneously in the carbonaceous agent.
    [0022] EXAMPLE 2 Preparation of several positive electrodes EA, EB, E-1 and E-2 Each of the composite materials A, B, 1 and 2 obtained in Example 1 was mixed at 80 ° C. for 30 minutes with tetraethylene glycol dimethyl ether (TEGDME), emeraldine salt (ES), lithium salt (LiTFSI) and N-methylpyrrolidone (NMP) in a mixer sold under the trade name Plastograph® EC by Brabender. The amount of NMP used represented at most about 30% by weight of the total mass of the composite material, TEGDME, ES and lithium salt.
    [0023] Each of the resulting pastes was then rolled at 95 ° C onto an aluminum current collector coated with a carbon-based layer. Each of the films thus obtained was dried at 105 ° C for 30 minutes to obtain a film positive electrode according to the invention. Table 2 below shows the mass composition of the four electrodes obtained: TABLE 2 TEGDME PANI S Black Salt Electrode Lithium Carbon (%) (%) (%) (%) (%) EA (*) 15.01 17 , 85 4.14 9.00 54.00 EB (*) 12.48 19.96 4.63 9.00 53.93 E-1 14.98 17.93 4.16 9.00 53.93 E- 2 15.00 17.85 4.15 9.00 54.00 (*): Electrode not forming part of the invention EXAMPLE 3 Manufacture of batteries comprising positive electrodes EA, EB, E-1 and E-2 a Preparation of a gelled polymer electrolyte EG according to the invention Lithium salt (LiTFSI) (39% by weight) was dissolved in TEGDME (6% by weight) with magnetic stirring at 50 ° C. Then, to the resulting mixture was added a copolymer of Zeospan® POE (20% by weight) and PVdF-co-HFP (35% by weight). The resulting mixture was kneaded in the Plastograph® EC mixer as described in Example 2 at 130 ° C for 1 hour. The electrolyte paste obtained was laminated at 125 ° C. between two silicone PET plastic films. b) Battery assembly Four BA, BB, B-1 and B-2 batteries were respectively prepared by assembling under an anhydrous atmosphere (air with a dew point <-40 ° C) by rolling at 5 bar and at 80 ° C. each of the four positive electrodes EA, EB, E-1 and E-2 obtained in Example 2, the gelled polymer electrolyte EG as obtained above in step a), and a negative electrode comprising lithium metal in the form of a lithium metal film approximately 100 amps thick.
    [0024] Table 3 below shows the different BA, BB, B-1 and B-2 batteries manufactured respectively with the positive electrodes EA, EB, E-1 and E-2 and the gelled polymer electrolyte EG: TABLE 3 Electrode Batteries Electrolyte Comments positive B-1 E-1 EG Battery forming part of the invention B-2 E-2 EG Battery forming part of the invention BA (*) EA EG Battery not forming part of the invention: composite material not according to the invention BB (*) EB EG Battery not forming part of the invention: composite material not according to the invention (*): Battery not forming part of the invention The specific capacity measurements during the discharge for batteries BA, BB, B-1 and B-2 are shown in FIG. 6, in which figure the specific capacitance (in mAh / g) is a function of the number of cycles with a current regime of 2 lithiums in 10 h. (- C / 10). In this FIG. 6, the specific capacity measurements during the discharge are made with respect to the sulfur mass. According to FIG. 6, batteries B-1 (curve with solid squares) and B-2 (curve with solid circles) forming part of the invention have an initial specific capacitance of approximately 550 to 600 mAh / g. , while BA batteries (curve with full diamonds) and BB (curve with solid triangles) not part of the invention have a lower initial specific capacitance of about 500 to 525 mAh / g. In addition, the cycling behavior of the B-A and B-B batteries is very insufficient since the specific capacity decreases drastically after 2 cycles.
    [0025] In particular, the specific capacity of the battery B-2 is stable over at least 10 cycles. These results show that the nature of the carbonaceous agent (e.g. porous structure) used to prepare the composite material is important, in order to obtain a high initial specific capacity and a good cyclability.
    [0026] EXAMPLE 4 Preparation of two positive electrodes E-3 and E-4 according to the invention A composite material 2 'was prepared as in Example 1, but with a mixture of S8 sulfur and Ketjenblack carbon black in mass proportions C / S: 18.8 / 81.2. Each of the composite materials 2 (obtained in Example 1) and 2 '(as defined above) was mixed at 80 ° C for 30 minutes with TEGDME, PEI or PVdF-co-HFP, LiTFSI , water (for the composite material 2) or NMP (for the composite material 2 ') in the Plastograph® EC mixer as described in Example 2. The amount of solvent used (water or NMP) represented at most 30% by weight of the total mass of the composite material mixture, TEGDME, PEI or PVdF-co-HFP, and LiTFSI.
    [0027] Each of the resulting pastes was then rolled at 95 ° C onto an aluminum current collector coated with a carbon-based layer. Each of the films thus obtained was dried at 105 ° C for 30 minutes to obtain a film positive electrode according to the invention. Table 4 below shows the mass composition of the two electrodes E-3 and E-4 forming part of the invention and obtained by the process described above: TABLE 4 Black electrode of LiTFSI TEGDME PVdF-co-PEI S carbon (HFP (0/0) (%) (%) (0/0)%) (%) E-3 12.5 20 3 10 0 54 E-4 15 3.9 15.1 0 12 54 25 EXAMPLE 5 Preparation of three positive electrodes EC, ED and EE not in accordance with the invention The positive electrode EC was prepared by extrusion of a mixture of powders of composite material 2 'obtained in Example 4, of lithium salt ( LiTFSI) and copolymer of the POE, then by rolling at 95 ° C of the paste thus obtained on an aluminum current collector coated with a carbon-based layer. The paste was then dried at 105 ° C for 30 minutes to obtain a film positive electrode not according to the invention. The positive electrode E-C does not form part of the invention since it does not contain a low molecular weight liquid linear polyether as defined in the invention. The positive electrode ED was prepared by extruding a mixture of S8 elemental sulfur, Ketjenblack carbon black, lithium salt (LiTFSI) and TEGDME low molecular weight liquid linear polyether followed by 95 ° rolling. C of the paste thus obtained on an aluminum current collector covered with a carbon-based layer. The paste was then dried at 105 ° C for 30 minutes to obtain a film positive electrode not in accordance with the invention. The positive electrode E-D does not form part of the invention since the mixture of sulfur agent and carbonaceous agent has not undergone pretreatment before the manufacture of the positive electrode. The positive electrode EE was prepared by extruding a mixture of elemental sulfur 58, Ketjenblack carbon black, lithium salt (LiTFSI) and POE copolymer, followed by rolling at 95 ° C. obtained on an aluminum current collector covered with a carbon-based layer. The slurry was then dried at 105 ° C for 30 minutes to obtain a film positive electrode not according to the invention. The positive electrode EE does not form part of the invention since it does not contain a low molecular weight liquid linear polyether as defined in the invention and that the mixture of sulfur agent and carbonaceous agent has no effect. not undergone pretreatment before manufacturing the positive electrode. Table 5 below shows the mass composition of the three electrodes EC, ED, and EE not forming part of the invention and obtained by the method described above: TABLE 5 LiTFSI LiTFSI Black Electrode PVdF-co- (% ) Carbon (%) Copolymer of POE HFP (%) (%) () (0/0) (%) EC (*) 15 6 25 10 0 54 ED (*) 7 17 0 20 3 54 EE (*) 5 9 16 16 0 54 (*): Electrode not forming part of the invention EXAMPLE 6 Manufacture of batteries comprising the positive electrodes EC, ED, EE, E-3 and E-4 a) Preparation of a polymer electrolyte According to the invention, lithium gelled salt (LiTFSI) (39% by weight) was dissolved in TEGDME (6% by weight) with magnetic stirring at 50 ° C. Then, to the resulting mixture was added a copolymer of Zeospan® POE (20% by weight) and PVdF-co-HFP (35% by weight). The resulting mixture was kneaded in the Plastograph® EC mixer as described in Example 2 at 130 ° C for 1 hour. The electrolyte paste obtained was laminated at 125 ° C. between two silicone PET plastic films. B) Preparation of a solid polymer electrolyte ES not in accordance with the invention The solid polymer electrolyte was prepared by extrusion of a mixture of lithium salt (LiTFSI) (12% by weight), of Zeospan POE copolymer ® (48% by weight) and PVDF-co-HFP (40% by weight), then by rolling the electrolyte paste obtained at 125 ° C between two silicone PET plastic films. c) Battery assembly Five BC, BD, BE, B-3 and B-4 batteries were prepared by laminating at 5 bar at 80 ° C and under anhydrous atmosphere (air with a dew point <-40). ° C): - each of the five positive electrodes EC, ED, EE, E-3 and E-4 obtained in Examples 4 and 5, - one of the ES or EG polymer electrolytes as obtained above 10 to step a) or b), and a negative electrode comprising lithium metal. Table 6 below shows the different batteries BC, BD, BE, B-3 and B-4 respectively manufactured with the positive electrodes EC, ED, EE, E-3 and E-4 and one of the electrolytes polymers ES or EG: 15 TABLE 6 Battery Electrode Electrolyte Comments Positive B-3 E-3 EG Battery part of the invention B-4 E-4 EG Battery part of the invention BC EC ES Battery not part of the invention: electrolyte and electrode not in accordance with the invention BD ED EG Battery not forming part of the invention: electrode not according to the invention BE EE ES Battery not forming part of the invention: electrolyte and electrode not in accordance with the invention The specific capacity measurements during the discharge for batteries BC, BD, BE, B-3 and B-4 are shown in FIG. 7, in which figure the specific capacitance (in mAh / g) is a function of the number 20 cycles with a current regime of 2 lithiums in 10 hours (- C / 10). In this figure 7, the specific capacity measurements during the discharge are made with respect to the mass of sulfur. According to FIG. 7, batteries E-3 (curve with solid black squares) and E-4 (curve with solid black circles) forming part of the invention respectively have an initial specific capacitance of about 210 and 490 respectively. mAh / g, and EC batteries (curve 5 with full gray triangles), ED (curve with full gray rhombuses) and EE (curve with solid black diamonds) not part of the invention respectively have an initial specific capacity about 290, 210 and 425 mAh / g. In addition, batteries B-C, B-D and B-E have a very inadequate cycling resistance since the specific capacity decreases drastically after 2 cycles. The specific capacity of E-3 e E-4 batteries is stable for at least 10 cycles. These results show that the combination of the pretreatment of the carbonaceous agent mixture and the sulfur-containing agent and the use of the gelled polymer electrolyte makes it possible at the same time to obtain a marked improvement in the initial specific capacity and the cyclability. . Thus, a true synergistic effect of the compositions of the positive electrode and of the electrolyte is observed, in particular at 100 ° C. (operating temperature of the battery in the examples of the invention).
    [0028] Indeed, when the gelled polymer electrolyte EG is replaced by a solid polymer electrolyte ES (battery B-C, curve with the gray solid triangles), the discharge capacity decreases after only a few cycles. In the same way, when the gelled polymer electrolyte EG is replaced by a solid polymer electrolyte ES and the pretreatment of the mixture of sulfur agent and carbonaceous agent is not carried out (battery BE, curve with the black diamonds full), the discharge capacity decreases drastically after only a few cycles. Likewise, the use of a gelled polymer electrolyte EG with a conventional positive electrode, that is to say without pretreatment of the mixture of sulfur-containing agent and carbon-containing agent (BD battery, curve with the solid gray diamonds ) gives similar results. On the other hand, the use of a positive electrode and an electrolyte both in accordance with the invention (battery B-3, curve with solid black squares) makes it possible to observe a stabilization and even a slight increase in the capacitance even after a larger number of cycles. Cyclability is therefore greatly improved thanks to the invention. FIG. 7 also shows that the addition in the positive electrode of a conductive polymer such as PEI makes it possible to guarantee a good cyclability of the battery while increasing by approximately 50% the value of the initial discharge capacity (battery B-4, curve with solid black circles).
    权利要求:
    Claims (21)
    [0001]
    REVENDICATIONS1. Composite material comprising sulfur (S) and carbon (C), characterized in that it is obtained according to the following steps: i) a step of mixing a substantially mesoporous carbonaceous agent and a sulfur-containing agent, the amount of sulfur (S) in said mixture ranging from 75% to 85% by weight, ii) a step of grinding the mixture obtained in the preceding step i), iii) a heat treatment step of the ground mixture obtained at preceding step ii) in a closed container, at a temperature sufficient to melt the sulfur, iv) a grinding step of the heat-treated mixture of the preceding step iii), and in that said carbonaceous agent used in step i) has the following characteristics: - an SBET specific surface greater than or equal to 700 m2 / g, said specific surface being calculated by the BET method, - an average mesopore size of between 4 and 10 nm, said size being calculated by the m BJH thode, - a total pore volume greater than or equal to 1 cm3 / g, said total pore volume being calculated by the BET method, said sulfur agent being chosen from elemental sulfur S8 and an organic sulfur compound comprising at least one SS bond .
    [0002]
    2. Composite material according to claim 1, characterized in that the carbonaceous agent is carbon black. 25
    [0003]
    3. Composite material according to claim 1 or claim 2, characterized in that the sufficient temperature of the heat treatment of step iii) is from 115 ° C to 270 ° C.
    [0004]
    4. Composite material according to any one of claims 1 to 3, characterized in that step iii) is carried out under dry air atmosphere.
    [0005]
    5. A positive electrode characterized in that it comprises: at least one composite material comprising sulfur and carbon and as defined in any one of claims 1 to 4, as electrode active material; at least one polymeric binder P1; at least one low molecular weight linear liquid polyether; and at least one lithium salt L1, and in which the sulfur (S) represents at least 40% by weight with respect to total mass of said positive electrode.
    [0006]
    6. Positive electrode according to claim 5, characterized in that it comprises from 2 to 20% by weight of liquid linear polyether low molecular weight, relative to the total mass of the positive electrode.
    [0007]
    7. Positive electrode according to claim 5 or claim 6, characterized in that the low molecular weight liquid linear polyether is chosen from: polyethylene glycols of formula H- [O-CH 2 -CH 2] m -OH, in which m is between 1 and 13, the glycol ethers of formula R- [O-CH 2 -CH 2] pO-R ', in which 20 p is between 1 and 13 and R and R', which are identical or different, are linear, substituted or cyclic alkyl groups, the ethers of formula R1- [CH2-0], 1-R1 ', in which q is between 1 and 13, R1 and R1', which are identical or different, are linear alkyls substituted or cyclic, cyclic ethers, cyclic polyethers, and mixtures thereof.
    [0008]
    8. Positive electrode according to any one of claims to 7, characterized in that the polyether is tetraethylene glycol dimethyl ether (TEGDME).
    [0009]
    9. Positive electrode according to any one of claims 5 to 8, characterized in that it comprises from 5 to 20% by weight of polymer binder P1, relative to the total mass of the positive electrode.
    [0010]
    10. Positive electrode according to any one of claims 5 to 9, characterized in that it comprises 2 to 25% by weight of lithium salt L1, relative to the total mass of the positive electrode.
    [0011]
    11. Positive electrode according to any one of claims 5 to 10, characterized in that the polymeric binder P1 is polyethyleneimine (PEI) or polyaniline in the form of emeraldine salt (ES). 10
    [0012]
    12. A method of manufacturing a positive electrode as defined in any one of claims 5 to 11, characterized in that it comprises the following steps: a) a step of mixing a composite material comprising sulfur and carbon and as defined in any one of claims 1 to 4 with at least one polymeric binder P1, at least one lithium salt L1, at least one linear low molecular weight polyether, and optionally at least one solvent said polymer binder P1, to obtain an electrode paste, b) a step of applying said electrode paste to at least one support, c) a step of drying said electrode paste to obtain a positive electrode in the form of a supported film.
    [0013]
    13. Process according to claim 12, characterized in that said solvent represents less than 30% by weight of the total mass of the mixture of composite material, polymer binder P1, lithium salt L1 and polyether.
    [0014]
    14. The method of claim 12 or claim 13, characterized in that step a) is carried out by extrusion or grinding.
    [0015]
    15. Lithium-sulfur battery, characterized in that it comprises: a positive electrode as defined in any one of claims 5 to 11 or as manufactured according to the process defined in any one of claims 12 to 14, - a metal negative electrode selected from lithium and a lithium alloy, - a gelled polymer electrolyte comprising at least one linear low molecular weight liquid polyether as defined in claim 7, at least one lithium salt L2 and at least one polymeric binder P2.
    [0016]
    16. The lithium-sulfur battery according to claim 15, characterized in that the gelled polymer electrolyte comprises from 20 to 45% by weight of lithium salt L2, relative to the total mass of the gelled polymer electrolyte.
    [0017]
    17. A lithium-sulfur battery according to claim 15 or claim 16, characterized in that the lithium salt L2 is chosen from lithium fluoride (LiFO3), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium lithium hexafluorophosphate (LiPF6), lithium fluoroborate (LiBF4), lithium metaborate (LiBO2), lithium perchlorate (LiCIO4), lithium nitrate (LiNO3), lithium bis (fluorosulfonyl) imide (LiFSI), and their mixtures. 20
    [0018]
    18. lithium-sulfur battery according to any one of claims 15 to 17, characterized in that the gelled polymer electrolyte comprises from 3 to 20% by weight of polyether, relative to the total mass of the gelled polymer electrolyte.
    [0019]
    19. lithium-sulfur battery according to any one of claims 15 to 18, characterized in that the gelled polymer electrolyte comprises from 40 to 80% by weight of polymer binder P2, relative to the total mass of the electrolyte. gelled polymer.
    [0020]
    20. lithium-sulfur battery according to any one of claims 15 to 19, characterized in that the polymeric binder P2 is selected from polyolefins such as homopolymers or copolymers of ethylene and propylene, or a mixture of at least two of these polymers; homopolymers and copolymers of ethylene oxide (e.g. POE, POE copolymer), methylene oxide, propylene oxide, epichlorohydrin or allyl glycidyl ether, or mixtures thereof; halogenated polymers such as homopolymers and copolymers of vinyl chloride, vinylidene fluoride (PVdF), vinylidene chloride, ethylene tetrafluoride, or chlorotrifluoroethylene, copolymers of vinylidene fluoride and hexafluoropropylene (PVdF -co-HFP) or mixtures thereof; anion-type electronic non-conductive polymers such as poly (styrene sulfonate), poly (acrylic acid), poly (glutamate), alginate, pectin, or mixtures thereof; polyacrylates; and one of their mixtures.
    [0021]
    21. A method of manufacturing a lithium-sulfur battery as defined in any one of claims 15 to 20, characterized in that it comprises the following steps: A) a step of preparation of a gelled polymer electrolyte such as defined in any one of claims 15 to 20; and B) a step of assembling a positive electrode as defined in any one of claims 5 to 11 or as manufactured according to the method defined in any one of claims 12 to 14, of a negative electrode and the gelled polymer electrolyte as obtained in the previous step A).
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    同族专利:
    公开号 | 公开日
    EP3116827B1|2018-01-31|
    WO2015136197A1|2015-09-17|
    US20180175375A1|2018-06-21|
    US10468670B2|2019-11-05|
    FR3018516B1|2019-08-23|
    EP3116827A1|2017-01-18|
    CN106537657B|2019-08-16|
    CA2941328A1|2015-09-17|
    ES2663543T3|2018-04-13|
    KR20170003534A|2017-01-09|
    JP2017509120A|2017-03-30|
    CN106537657A|2017-03-22|
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    法律状态:
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    2017-03-22| PLFP| Fee payment|Year of fee payment: 4 |
    2018-03-23| PLFP| Fee payment|Year of fee payment: 5 |
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    2020-12-18| ST| Notification of lapse|Effective date: 20201110 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452087A|FR3018516B1|2014-03-13|2014-03-13|LITHIUM SULFUR BATTERY|
    FR1452087|2014-03-13|FR1452087A| FR3018516B1|2014-03-13|2014-03-13|LITHIUM SULFUR BATTERY|
    CA2941328A| CA2941328A1|2014-03-13|2015-03-09|Lithium-sulfur battery|
    EP15714588.9A| EP3116827B1|2014-03-13|2015-03-09|Lithium-sulfur battery|
    PCT/FR2015/050568| WO2015136197A1|2014-03-13|2015-03-09|Lithium-sulfur battery|
    KR1020167028472A| KR20170003534A|2014-03-13|2015-03-09|Lithium-sulfur battery|
    ES15714588.9T| ES2663543T3|2014-03-13|2015-03-09|Lithium sulfur battery|
    CN201580013779.3A| CN106537657B|2014-03-13|2015-03-09|Lithium-sulfur cell|
    JP2016555835A| JP2017509120A|2014-03-13|2015-03-09|Lithium sulfur battery|
    US15/125,457| US10468670B2|2014-03-13|2015-03-09|Lithium-sulfur battery|
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