• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to the field of Li / S batteries. More particularly, the invention relates to an active material for the manufacture of an electrode, comprising carbon nanofillers dispersed in a sulfur-containing material, the active material being obtained by a melt process. The amount of carbon nanofillers in the active ingredient represents 1 to 25% by weight relative to the total weight of the active ingredient. The active material according to the invention makes it possible to improve the electronic conductivity of the formulation of the electrode. Another aspect of the invention is the use of the active material in an electrode, particularly in a Li / S battery cathode.
    公开号:FR3030890A1
    申请号:FR1463052
    申请日:2014-12-22
    公开日:2016-06-24
    发明作者:Alexander Korzhenko；Christophe Philippe Vincendeau
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to the field of Li / S batteries. More particularly, the invention relates to active material for the manufacture of an electrode, comprising carbon nanofillers dispersed in a sulfur material, the active material being obtained by a molten process. STATE OF THE ART A lithium / sulfur accumulator (hereinafter referred to as Li / S battery) consists of a positive electrode (cathode) of elemental sulfur or of another electroactive sulfur material, a negative electrode, (a) lithium metal ion or a lithium metal alloy, as well as an organic electrolyte. Typically, the positive electrode is prepared from an active material comprising sulfuric acid (hereinafter referred to as "native" p.), And optionally of various additives, mixed with a solvent. and thus forming a paste which is applied to a current collector and then dried to remove the solvent. The formed composite structure is optionally subjected to a compression step, then cut to the desired size of the cathode. Li / S is obtained by depositing a separator on the cathode, then a lithium anode is deposited on the separator. An electrolyte generally comprising at least one Tm salt dissolved in a solvent is then introduced into the b: Itterie. F 's batteries have been the subject of much research since 2000 and are seen as promising alternatives to conventional Li-ion batteries. The interest of this type of battery comes from the strong capacity of mass storage of the sulfur electrode. allowing to reduce energy up to 500 Wh.kg-I. In addition, sulfur has the significant advantages of being plentiful, low cost and non-toxic, allowing for the development of large scale Li / S batteries.
    [0002] The discharge and charge mechanism of a Li / S battery is based on the reduction / oxidation of sulfur at the cathode (S + 2e- * ->: S2-) and the oxidation / reduction of lithium at the anode ( Li 4-> Li + er). During the course of the deposition, the sulfur molecules S are reduced and form chains of polysulfides of thium, of the general formula Li 2 Sn (n: 2): 21. solubilized in the organic electrolyte. The last sulfur reduction step consists of the formation of Li2S lithium sulfide which precipitates in the organic electrolyte and settles on the anode. Inverse electrochemical charges occur under load. In order to allow electrochemical reactions to occur rapidly at the electrodes, the cathode and the anode must be generally good electronic conductors. Since sulfur is an electronic insulator (c3 = 5.10-3 ° S.cm-1 at 25 ° C), the rates of release are relatively slow. Different ways of improving the electronic conductivity of the active material are envisaged, in particular (addition of an electronic conductive additive to a conductive carbonaceous material, but the kinetics of reaction at the cathode of the jet). If the sulfur / additive mixture is not optimal or if the additive content is too low, among the conductive additives, carbon black, activated carbon, carbon fibers or nanotubes (ie carbon are Generally used Carbon black is conventionally used The mixture of the active ingredient and the conductive additive can be done in different ways, for example, the mixing can be done directly during the preparation of the electrode. It is then mixed with the conductive additive and the wafer by mechanical stirring, before shaping of the electrode.Through this homogenization step, the additroHoe is supposed to be distributed around the particles of SOU irc, and thus create a network pe-colttrt: A grinding step can also be used and allows to obtain a more intimate mixture of materials. However, this additional step may result in destruction of the porosity of the electrode.
    [0003] Another way of mixing the active ingredient with the carbonaceous additive consists in grinding the sulfur and the carbonaceous additive in the dry process, so as to coat the carbon sulphate.
    [0004] In the same context, the carbon can be deposited around the sulfur particles by vapor deposition. Conversely, a core-shell structure may also be prepared from carbon black on which a layer of sulfur is deposited, for example by precipitation of sulfur on carbon black nanoparticles.
    [0005] Unlike carbon black, additives of the carbon nanotube (CNT) type have the advantage of also conferring a beneficial adsorbent effect for the active ingredient by limiting its dissolution in the electrolyte and thus promoting better cyclability. However, the introduction of CNTs into the formulations constituting the electrodes still raises many problems. In fact, CNTs are difficult to handle and to disperse, because of their small size, their powderiness and, possibly, when they are used, by chemical vapor deposition (CVD), of their structure, and in other words their geriatric structure. strong Van Der Waals interactions between their molecules. The low dispersion of the NTCs limits the efficiency of the charge transfer between the positive electrode and the electrolyte and thus the formation of the LUS battery despite the addition of the conductive material. Therefore, it would be advantageous for the formulator to have an active ingredient comprising CNTs well dispersed in sulfur, and more generally in a sulfur-containing material, in the form of ready-to-use active ingredient, which can be used directly into a formulation for the manufacture of a Li / S battery electrode in order to effectively increase its electronic conductivity. However, the Applicant has discovered that this need could be satisfied by bringing CNTs into contact with a sulfur-containing material in the melting process in a compounding device, thus forming an improved active material that can be used for the preparation of an electrode. It also appeared that this invention could also be applied to other carbon nanofillers than CNTs, in particular to carbon nanofibers, and graphene, or their melanites in all proportions.
    [0006] SUMMARY OF THE INVENTION The object of the invention is to provide an active material for the manufacture of an electrode which is a sulfur material; from 5 to 25% by weight of carbon nanofillers dispersed in the sulfur material; said active material being obtained by molten route.
    [0007] By "carbon nanobond" is meant a charge comprising at least one member of the group consisting of carbon nanotubes, carbon nanofibers and graphene, or a mixture thereof in all proportions. Preferably, the carbon nanofillers comprise at least carbon nanotubes.
    [0008] By "sulfur-containing material" is meant a sulfur-donor compound chosen from native (or elemental) sulfur, sulfur-containing organic compounds or polymers and sulfur-containing inorganic compounds. According to a preferred embodiment of the invention, the sulfurized material comprises at least native sulfur, the sulfurized sulfuric acid being native sulfur alone, or in admixture with at least one other sulfur material. The active ingredient according to the invention is obtained by a melt process, that is to say that it comprises carbon nanofillers well percolated in a molten sulfur matrix. The sulfur material / nanofiller mixture is of morphology adapted to an optimization of the functioullenlenilt of a Li / S battery electrode.
    [0009] The active material according to the invention can thus ensure efficient electricity transfer from the current collector of the electrode and provide the active interfaces of 1 × electrochemical reactions during operation of the battery. Thus, the present invention provides an active nrc having a better combination of a sulfur donor material, and carbon nanofillers particles to facilitate access of sulfur to electrochemical reactions. In addition, the electrode incorporating the active material .sclon the invention procii.c uni good maintenance of the operation of the battery during icmps. According to one embodiment of the invention, the active material further comprises at least one additive selected from a rheology modifier, a binder, an ionic conductor, a carbonaceous electrical conductor, an electron donor element or their combination. Like carbon nanofillers, the additives are incorporated into the active ingredient by the molten route. Another aspect of the invention is the use of the active material as described above in an electrode, in particular in a Li / S battery cathode. The active material according to the invention makes it possible to improve the electronic conductivity of the formulation of the electrode. DESCRIPTION OF THE INVENTION The invention is now described in more detail and without limitation in the description which follows. The carbon nanofillers According to the invention, the carbon nanofillers are carbon nanotubes, carbon nanofibers, graphene, or a mixture of these in all proportions. Preferably, the carbon nanofillers are carbon nanotubes, alone or in admixture with at least one other carbon nanofiller. The carbon nanotubes (CNTs) used in the composition of the active material may be of the single-wall, double-wall or wall type. The carbon nanotubes used according to the invention usually have a mean diameter ranging from 0.1 to 200 nm, preferably from 0.1 to 100 nrn, more preferably preferably from 0.4 to 50 nm and better still from 1 to 30 nm, indeed from 10 to 15 nm, and advantageously a length of more than 0.1 μm and advantageously of 0.1 to 20 μm, preferably of 0 , 1 to 10 μm, for example about 6 μm. Their length / diameter ratio is advantageously greater than 10 and most often greater than 100. Their specific surface area is, for example, between 100 and 300 m 2 / g, advantageously between 200 and 300 m 2 / g, and the density is in the range from 100 to 300 m 2 / g. in particular between 0.01 and 0.5 g / cm3 and more preferably between 0.07 and 0.2 g / em3. MWNT may for example comprise from 5 to 15 sheets, more preferably from 7 to 10 sheets. The carbon nanclubes are in particular obtained by vapor phase deposition, for example according to the method described in the document WO 06/082325. Preferably, they are obtained to punish renewable raw material, in particular of vegetal origin, as (IL: cry: in the patent application EP 1980530. These nanotubes may or may not be treated.An example of crude carbon nanotubes is The nanotubes can be purified and / or treated (for example oxidized) and / or milled and / or functionalised The grinding of the nanotubes may be not n; The invention relates to cold-rolled or hot-melt processes carried out according to the known techniques described above, such as ball mills, hammer mills, grinding mills, knives mills, jet mills or any grinding system capable of reducing size of the entangled network of nanotubes This grinding step is performed according to a technique of grinding by gas jet and in particular in an air jet mill The purification of the raw or milled nanotubes can be realized This is done by washing with a sulphuric acid solution, in order to rid them of any residual mineral and metal impurities, such as, for example, iron from their prepregnation process. The weight ratio of nanotubes to sulfuric acid can in particular be between 1: 2 and 1: 3. The purification operation may also be carried out at a temperature ranging from 90 to 120 ° C, for example for a period of 5 to 10 hours. This operation can advantageously be followed by water and drying steps of purified nin. I a ria lotubes may alternatively be purified by high temperature heat treatment, typically above 1000 ° C. The oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite containing from 0.5 to 15% by weight of NaOCl and preferably from 1 to 10% by weight of NaO Cl, for example in a weight ratio of nanotubes to sodium hypochlorite ranging from 1: 0.1 to 1: 1. The oxidation is conveniently carried out at a temperature below 60 ° C and preferably at room temperature for a few minutes to 24 hours. This oxidation operation may advantageously be followed by filtration steps and / or e: centrifugation, washing and drying of the oxidized nanotubes. The functionalization of the nanotubes can be carried out by grafting reactive units, such as vinyl monomers on the surface of the nanotubes.
    [0010] Preferred raw carbon nanotubes are preferably milled, i.e., nanotubes which are neither oxidized nor purified nor functionalized and have not undergone any other chemical and / or thermal treatment. The carbon nanofibers usable as carbon nanofillers in the present invention are, like the carbon nanotubes, nanofilaments produced by chemical vapor deposition (or CVD) from a carbon source is decomposed on a catalyst comprising a transition metal (Fe , Ni, Co, Cu), in the presence of hydrogen, at temperatures of 500 to 1200 ° C. However, these two carbonaceous charges are differentiated by their structure, because carbon nanofibers consist of grap zones. ticks more or less organécs (or terhostratiques stacks) whose planes are inclined at variable angles with respect to the axis of the fiber. These stacks may take the form of platelets, fish bones or stacked cups to form structures having a die-meter generally ranging from 100 nm to 500 nm or more.
    [0011] Examples of usable carbon nanofibers have in particular a diameter of 100 to 200 μm, for example about 150 nm, and advantageously a length of 100 to 200 μm. For example, the VGCF® nanofibers of SF1OWA DEN may be used. O. By graphene, one deiane a sheet of vintage pl: the plan, isolated and individualized, but also, by ibLun, an assembly comprising between one and a few tens of sheets and having a flat structure or more or less wavy. This definition thus includes the F'1, G (Few Layer Graphene or gi .- 'nnnc., Slightly stacked), the NGP (Nan.osized Geap_n Plates or gi Dbèrie plates, the nanometric dimension), the CNS (Carbon - N -., NiJoSheets or nano-graphene), GNR (Graph.ene NanoRibbons or graphene nano-ribbons). On the other hand, it excludes carbon nanotubes and nanofibers, which consist respectively of the winding of one or more sheets of graphene in a coaxial manner and the turbostratic entanglement of these sheets. It is furthermore preferred that the graphene used according to the invention is not subjected to an additional chemical oxidation or functionalization step.
    [0012] The graphene used according to the invention is obtained by chemical vapor deposition or CVD, preferably by a process using a powdery catalyst based on a mixed oxide. It is typically in the form of particles having a thickness of less than 50 nm, preferably less than 15 nm, more preferably less than 5 nm and less than one micron side dimensions, preferably 10 nm less than 1000 nm, more preferably 50 to 600 nm, or even 100 to 400 nm. Each of these particles contains in L: al from I to 50 sheets, preferably from 1 to 20 sheets and more preferably from 1 to 1.0 leaflets, or even 1 to 5 leaflets which are likely to be dissociated from each other in the form of independent leaflets, for example during an ultrasonic treatment. The sulfuric material may be sulfurized, sulfur-containing organic compound or polymer, or a sulfur-containing inorganic compound, or a mixture thereof in all proportions. Different sources of native sulfur are commercially available. The particle size of the sulfur powder can vary widely. Sulfur can be used as is, or the sulfur can be previously purified by different techniques such as refining, sublimation, or precipitation. Sulfur, or more generally the sulfurized material, can be subjected to a preliminary grinding and / or sieving step in order to reduce the size of the particles and to tighten them. The inorganic sulfur compounds that can be used as sulfur-containing materials are, for example, anionic metal polysulphides. alkali, preferably lithium polysulfides represented by the formula Li2Si (with n> 1). organic sulfur compounds or polymers which can be used as retort, materials. The compounds may be selected from organic organic polysulfides including, for example, functional groups such as acetal, dithiocetad or trithioorthocarbonate, aromatic polyunsulfides, polyetherpolysers, polysulfuric acid salts, and the like. thiosulfonales [-S (O) 2 -S-1, thiosulfinates [-S (O) -S-], thiocarboxylates [-C (O) -S-], dithiocarboxylates [- RC (S) -S -], thiophosphates, thiophosphonates, thiocarbonates, polysulfides oranometallic, or mixtures thereof. Examples of such organo-sulfur compounds are described in particular in document WO 2013/155038.
    [0013] According to one particular embodiment of the invention, the material is -c. is a polysu 'tere friend'. unique. The aromatic polysulfides correspond to the general formula (in which: R 1 to R 3 represent, in a hydrogen or a hydrogen radical, a radical -OH or -O-1 -vr, or saturated carbon or urea containing from 1 to 20 carbon atoms, or a group --OR10, with R19 being alkyl, aryialkylc, acyl, carboalkoxy, alkyl ether, silyl, silyl alkyl, having 1 to 20 carbon atoms, an alkali metal or alkaline earth metal - n and n 'are two integers, identical or different, each being greater than or equal to 1 and less than or equal to 8, - p is an integer between 0 and 50, - and A is a nitrogen atom, a single bond, or a sauirec or unsaturated carbon chain of 1 to 20 carbon atoms, preferably in formula (I): R1, R4 and R7 are radicals R5 and R8 are hydrogen atoms, R3, R6 and Ry are saturated or unsaturated carbon chains having from 1 to 20 carbon atoms, preferably from 3 to 5 carbon atoms, the average value of n and n is about 2, the average value of p is between 1 and 10, from: 3 and 8. (These average values are calculated by those skilled in the art from proton data and by sulfur dioxide assay). 0 - A is a single bond linking sulfur atoms to aromatic rings. Such poly (alkyl phenol) polysulfides of formula (I) are known and can be prepared for example in two steps: 1) reaction of monochloride or sulfur dichloride on a yl-t-17énol, at a temperature included between 100 and 200 ° C, according to the ante: OH s2cI2 or SCI2 (II) The compounds of formula (II) are sold especially by the company ARKEMA under the name VULTAC®. 2) reaction of the compound (II) with a metal derivative containing the metal M, such as for example an oxide, a hydroxide, an alcoholate or a dialkylamide of this metal to obtain 0-M radicals.
    [0014] According to a more preferred variant, R is a tert-butyl or tert-pentyl radical. According to another preferred variant of the invention, a mixture of. compounds of formula (I) wherein 2 R radicals present on each aromatic unit are carbon chains comprising at least one tertiary carbon through which R is connected to the aromatic ring. The active ingredient The qunntiLr of carbon nanofillers in the active ingredient rcprescn.c (1 to 25% by weight, pr: Teterice 10 to 15% by weight, for example 12 to 14% by weight, relative to the LeLLI of the active ingredient, the carbonaceous compounds, such as CNTs, are mixed with the sulfur, in part, with sulfur, in the molten state, but the melting of the mixture is limited by the difference in density. between the CNTs (0.1 g / cm) and the sulfur (2 is necessary to add an intense mechanical energy to achieve this nge.To do this, it is a compounding device, that is to say a device classically As used in the plastics industry for the thermoplastic polymers and additives for the production of coatings, the active ingredient according to the invention can be prepared according to a process in the following steps. the introduction into a compounding device of at least one sulfur-containing material, and carbon nanofillers, (b) melting the sulfur material; (c) mixing the molten sulfur material and the carbon nanofillers; (d) recapping the resulting mixture into agglomerated solid physical form; (e) grinding the mixture into powder form. In a composite apparatus, the sulfur material and the carbon nanofillers are mixed using a high shear device, for example a co-rotating twin-screw extruder or a co-kneader. The molten material generally comes out of the apparatus in solid physical form agglomerated, for example in the form of granules, or in the form of rods which, after cooling, are cut into granules. Examples of co-kneaders are the BUSS® MDK 46 co-kneaders and those of the BUSS® MKS or MX series, marketed by the company BUSS AG, or all consist of a screw shaft provided with fins, arranged in a sheath. If it consists of several parts and d: the inner wall is provided with kneading teeth adapted to cooperate with ai'utus to produce a shear of the kneaded material. The shaft is a recess, and provided with an oscillation movement in the axial direction, by a motor. These co-kneaders 30 may be equipped with a granule manufacturing system, adapted for example at their outlet, which may be an extrusion screw or a pump.
    [0015] The usable copolymers preferably have an L / D screw ratio of from 7 to 72, for example from 10 to 20, while the co-rotating extruders advantageously have a UD ratio of from 15 to 56, for example at 50. The compounding step is carried out at a temperature above the melting point of the sulfur material. In the case of sulfur, the compound temperature can be from 120 ° C to 150 ° C. In the case of other types of sulfurized material, the compounding temperature is a function of the specifically used material, the melting temperature of which is generally mentioned by the supplier of the material. The residence time will also be adapted to the nature of the sulfur material.
    [0016] This method makes it possible to efficiently and homogeneously disperse a large amount of carbon nanofillers in the sulfurized material, despite the difference in density between the constituents of the active material. According to one embodiment of the invention, the active material further comprises at least one additive selected from a rheology modifier, a binder, an ionic conductor, a carbonaceous electrical conductor, an electron donor element or their combination. These additives Cs are advantageously introduced during the compounding step, so as to obtain a homogeneous active material. In this embodiment, the sulfurized material and the carbonaceous nanofillers then represent from 20% to 100% by weight, preferably from 20% to 80% by weight relative to the total weight of the active material. In particular, it is possible to add, during the compounding step, a melt sulfur rheology modifier, in order to reduce the self-heating of the mixture in the compounding apparatus. . Such additives having an acidifying effect on the liquid sulfur are disclosed in WO 2013/178930. Examples which may be mentioned are dimethyl sulfide, diethyl sulphide, dipropyl sulphide, dibutyl sulphide, dimethyl disulphide, diethyl disulphide, dipropyl disulphide and dibutyl disulphide. their trisulfide homologs, their tetrasulfide counterparts, their pentasulfide counterparts, their hexasulfide counterparts, alone or as mixtures of two or more of them in all proportions.
    [0017] The amount of rheology modifier additive is generally from 0.01% to 5% by weight, preferably from 0.1% to 3% by weight, based on the total weight of the active ingredient. The active material may comprise a top, such as a pot binder; mother. for example, among the Iiai.ugen polymers. LIC denotes fluorinated polymers, functional polyolefins, polyacrylonitriles, polyurethanes, polyacrylic acids and their derivatives, polyvinyl alcohols and polyethers, or a mixture thereof in all proportions. Examples of fluorinated polymers include polyvinylidene fluoride (PVDF), preferably in the form of CL, poly (trifluoroethylene) (PVF3), polytetrafluoroethylene (PTIE), copolymers of vinylidene fluoride with either hexanoropropylene (HEP), trifluoroethylene (VF3), tetrafluoroethylene (TFE) or chlorotrifluoroethylene (CTEFE), fluoroethylenpropyl (HEP) copolymers, copolymers of ethyl with either fluorothyiene / propylene (FEP), tetrafluoroethylene (TFE) or chlorotrifluoroethylene (CTEE); Perfluorup. vinyl ether (PPVE), perfluoroethyl vinyl ether (PEVE), 2,3,3,3 terratronitrile, and copolymers of ethylene with perfluoroethyl vinyl ether (PMVL), or mixtures thereof. By way of examples of polyethers, mention may be made of alkylene polyoxides such as POE ethylene polyoxides, polyalkylene glycols such as polyethylene glycols PEG, polypropylene glycols PPG, poly-triamethylene glycols (PTMCTs), polytetramethylene ethers glycols (PTMEG), etc. Preferably, the binder is .PVDF or POE. The active may corrode an ionic conductor having a surface on the surface of the supporting material in order to increase the ionic conductivity of the active material. Examples of ionic conductors that may be mentioned, in a non-limiting manner, are butadithium salts, for example lithium imidazolate salts, or lithium sulphites. Alkylene polyoxides which, in addition to their binder function, can also provide ionic conductivity properties to the active ingredient are also mentioned. The material acth, c may comprise an electrical conductor, advantageously a conductor ée carbon, such as carbon black, graphite or graphene, e: -alement in proportions ranging from 1 to 10% compared to the material scnifré . Preferably, the carbon black is used as the electrical conductor. The active ingredient may include an electron donor element to enhance the exchange and control of the polysulfide charge during charging. .1 cycles of charging / discharging the battery. As electron donor elements, it is advantageous to use an element, in the form of a powder or in the form of a salt, of columns IVa, Va and VIa of the periodic table, preferably chosen from Se, Te, Ge, Sn, Sb, Bi The active material according to the invention is advantageously in the form of a powder comprising: particles having a mean size of less than 150; preferably less than 100 μm, a median diameter of between 1 and 60 μm, preferably between 10 and 60 μm, more preferably between 20 and 50 μm, and a median diameter d 90 of less than 100 μm, these characteristics being determined by laser diffraction. In order to obtain this powder morphology, a hammer mill, brush mill, ball mill, an air jet mill, or other methods of micronization of solid materials are generally used. The active ingredient of the invention can be used to prepare a battery electrode. L Ale is generally in the range of 20 to 95% by weight, preferably 35 to 80% by weight based on to the complete formulation of the electrode. The invention will now be illustrated by the following examples, which are not intended to limit the scope of the invention as defined by the appended claims. EXPERIMENTAL PART Example 1: Preparation of an active ingredient S / NTC NTC (Graphistrength® C100 from ARKI7vr ./ ) and solid sulfur (50-800 1.1m) were introduced into the first feed hopper S / NTC a BUSS® MDK 46 co-malaxcur (L / D = 11), equipped with resuspension extrusion and a granulation device. Temperature setpoints within the co-kneader were as follows: Zone: 40 ° C; Zone 2: I 30 ° C; Screw: 120 ° C.
    [0018] At the exit of the die, the mixture ccrA, 87.5% by weight of sulfur and 12.5% by weight of CNT is in the form of granules obtained by cutting at the top, cooled by air. The granules were then ground in a hammer mill, cooling being provided by nitrogen. Observation under a scanning electron microscope showed that CNTs were well dispersed in sulfur. The granules were milled in a high speed brush mill (12,000-14,000 rpm), the chill pellets being made with liquid nitrogen at -30 ° C fed to the mill feed screw. The powder was screened using a cylindrical 80um grid. The particle size distribution by laser diffraction on a Malvern-type apparatus is shown in Figure 1. The largest particle size is less than 100 μm, and the median diameter d53 is between 20 and 50 μm. This powder consisting of 87.5% by weight of sulfur and 12.5% by weight of CNT is an active material that can be used for the preparation of a Li / S battery electrode. Preparation of an S / DMDS / NTC Masterbatch NTC (ARKEMA Graphist C100) and solid sulfur (50-800 μM) were introduced into the feed hopper of a co-polymer. BUSS® 25 MDK mixer. 46 (L / D = 11), equipped with a recovery extrusion screw and a granulation device. Liquid dimethyl disulfide (DMDS) was injected into the zone of the kneader. The temperature values within the co-kneader were as follows: Zone 30: 140 ° C: ZnL '2: 130 ° C; Screw: 120 ° C.
    [0019] At the exit of the die, the masterbatch consisting of 83% by weight of sulfur, 2% by weight of DN1DS and 15% by weight of CNT is in granules obtained by cutting at the head, cooled by a jet of water . The granules obtained were dried to a moisture content <100 ppm.
    [0020] The dry granules were then milled in a hammer mill, cooling being provided by nitrogen. A powder having a median diameter D 50 of between 30 and 60 μm was obtained which can be used for the preparation of a Li / S battery electrode. : Preparation of a poly (tert-butyl pflulioi) / NTC masterbatch of NTC (Graphistrengte C100 from ARKEMA) and solid sulfur (50-800 μm) were introduced into the first BUSS ') MDK 46 feed hopper (L / D = 1i), equipped with a recovery extrusion screw and a granulation device. Liquid dimethyl disulfide (DMDS) was injected into the comaller zone. The poly (tert-butyphenol) disulphide commercially known under the name VULTAC-TB7 from Arkema, is used with a Li salt, marketed under the name LOA (Lithium 5: 5-dicyano). -2- (trifluoromethyl) imidazole) by Arkema then introduced into the first hopper using a 3rd metering device. Temperature setpoints within the co-kneader were as follows: Zone: 140 ° C; Zone 2: 130 ° C; Screw: 120 ° C. At the exit of the die, the mixture is in the form of rLrw i obtained by cutting at the head, cooled by a jet of water. The granules obtained were dried to a moisture content <100 ppm. The granules were then milled in a hammer mill, the cooling being provided by nitrogen. A powder consisting of 77% by weight of sulfur, 2% by weight of DMDS and 15% by weight of CNT, 5% of VULTAC-TB7® I% of LOA, was obtained which can be used for the Li / S battery preparation. .
    [0021] EXAMPLE 4 Preparation of the Active Ingredient S / POE / LilS / 1 ITC NTCs (C: C100 from ARKEMA) and solid sulfur (50-800 μM) were introduced into the feed hopper of a carbomer. BLISS® 1VEDK 46 blender (L / D = 11), equipped with a recovery extrusion screw and a granulation device. POLYO, C WSR N-60K poly (ethylene oxide) (produced by DOW) was premixed with Li, S provided SIGMA. This mixture is introduced into the hopper by the 3rd feeder. The temperature readings within the co-kneader were as follows: Zone 1: 140 ° C .; Zone 2: 130 ° C; Screw: 120 ° C. At the outlet of the die, the mixture consisting of 70% by weight of sulfur, 15% of CNT, 10% of POLYOX® WSR N-60K, and 5% of Li2S is in the form of granules obtained by the scale of the rod, cut by the treadmill without contact with water. The dry granules were then milled in a hammer mill, the cooling being provided by nitrogen. There was obtained a powder consisting of 70% sulfur, 15% NTC, 10% POLYOX® WR N-60K, and 5% LI, S comprising particles having an average size of less than 150 μm. median diameter D50 and D90 adapted for that powder as cathode active material for battery LUS. EXAMPLE 5 Evaluation of Active Active substance evaluation tests were performed in a LUS battery model containing: 1) Li-metal anode, 100 μm thick; 2) Separator / membrane (20 p .... n) 3) Sulfolane base electrolyte with 1M Li 4) Cathode based on a sulfur formulation supported by an Al collector Two cathode formulations were tested: reference formulation comprising by weight 70% sulfur, 10% carbon black and 20% POE (POLYOX® WSR N-60K). Formulation comprising, by weight, 80% of active material of Example 1, 5% of carbon black and 15% of POE.
    [0022] The cathode formulation was applied to the electrode via a paste in a solvent and then dried. The cathode capacity of the test cell is between 1.5 and 3 mAh / cm. The test cells were put under charging / discharging conditions. The cathode performances were evaluated after 150 cycles: cathode prepared from the reference formulation: 78% with respect to the initial cathode capacity prepared from the formulation comprising the active ingredient according to the invention; These results confirm that the active ingredient according to the invention, comprising carbon nanofillers, makes it possible to improve the service life and therefore the efficiency of a Li / S battery.
    权利要求:
    Claims (8)
    [0001]
    REVENDICATIONS1. An active material for the manufacture of an electrode comprising: a sulfurized material, from 1 to 25% by weight of carbon nanofillers dispersed in the material, said active material being obtained by molten route.
    [0002]
    2. Active material according to claim 1, characterized in that the carbon nanofillers are chosen from carbon nanotubes, carbon nanofibers, graphene, or a mixture thereof in all proportions, preferably nanofillers. carbonaceous are carbon nanotubes.
    [0003]
    3. -ter've material according to claim 1 or 2, characterized in that the sulfur-containing material is a sulfur-containing sulfur compound selected from native sulfur, sulfur-containing organic compounds or polymers, or sulfur-containing inorganic compounds, or a sulfur-containing sulfur compound. mixture of these in all proportions.
    [0004]
    4. The active ingredient as claimed in claim 3, characterized in that the sulfur-containing inorganic compounds are alkali metal anionic polysulfides, with reference to lithium polysulfides represented by the formula Li / S, with n> 1.
    [0005]
    Active material according to claim 3, characterized in that e. CRI C. the sulfur-containing group is chosen from organic polysulfides, polythiolates including, in particular, functional groups such as dithioacetal, ditiliocetal or trithioorthoarbonate, aromatic polysulfides, polyether-polysulfides, iolysulfide salts, thiosulfonates [-S (O) 2 -S-], thiosulfates [-S (O) -S-], thi [- (-) - boxylates [-C (O) -S-], dithiocarboxylates [-RR (S) -S-], thosphates, thiophosphonates, thiocarbonates, organonenium polysulfides, or mixtures thereof.
    [0006]
    6. Active material according to claim 5, characterized in that the soured material is an aromatic polysulfide corresponding to the following general formula (I): Sn '- A in which: R1 to R9 represent, in the same or different manner, a hydrogen atom, a -OH radical or, or a saturated or unsaturated carbon chain having from 1 to 20 carbon atoms, or a group -OR.10, with R10 possibly being an alkyl radical. avialkyic. acvic, e: irboalkoxy, alkyl ether, silyl, silyl alkyl, having from 1 to 20 carbon atoms. M represents methanol or alkaline-tcrreent and n 'are identical or different, each being greater than or equal to 1 and equal to 8, p is an integer between 0 and 50; and A is a nitrogen atom, a single bond, or a saturated carbon chain or the 1 to 20 carbon atoms.
    [0007]
    7. The active ingredient according to any one of the preceding claims, characterized in that the rna comprises at least native sulfur.
    [0008]
    8. Active material according to any one of the preceding claims, characterized in that it further comprises at least one ad.diTif selected from a rheology modifier, a lianL, an ionic conductor, a carbonaceous electrical conductor, a donor element of electrons or their association. according to claim 8, characterized in that the modifier is dimethyl sulfide, diethyl sulfide. dipropyl sulphide, dibutyl sulphide, dimethyl disulfide. diethyl disulphide, dipropyl disulfide, dibutyl disulfide, their trisulphide counterparts, their tetrasulfide counterparts, their pentasulfide counterparts, their hexasulfide counterparts, alone or in mixtures of two or more of them in all proportions. 10. Aetive material according to claim 8, characterized in that the binder is selected from halogenated polymers, preferably fluorinated polymers, functional polyolefins, and polyethers, or a rneanee thereof in all proportions. 11. Active material according to the reyencileation 8, caraetérisée in that the binder is a fluoropolymer chosen from poly (vinylidene fluoride) (PVDF), preferably in form a, poly (trifluoroethylene) (PVF3), polytetrafluoroethylene (PTFE), copolymers of vinylidene fluoride with either Ellexafluoropropylene (HEP) or trifluoroethylene (VF3), or tetrafluoroelylen (TFE), or chlorotrifluoroethylene (CTEE), fluoroethylene / propylene copolymers (FEP), copolymers of ethylene with either illuornethylene / propylene (FEP), tetrafluoroethylene (TFE) or chlorotriflu: .-) ro. 11: 1 :); perfluoropropyl vinyl ether (PPVE, perfluoro (1 -VE), 2,3,3,3-tetrafluoropropylene, and ethylene copolymers with perfluoromethylvinyl ether (PMVE), or mixtures thereof. Active material according to claim 8, characterized in that the binder is a polyether chosen from alkylene polyoxides or polyaluminols.Active material according to claim 8, characterized in that the conductor e and an organic lithium salt such as a lithium imidazolate salt, a titiium sulphite, or an alkylene polyoxide 14. An active polymer according to claim 8 characterized in that the carbonaceous conductor is carbon black, graphite or graphene 15, active material according to the coating 8, characterized in that the electron donor element is an element, in the form of a powder or in the form of solvents, of 30, Va and Via periodic table, preferably selected from Se, Te, Ge, Sn, Sb, Bi , Pb, Si or As. 16. Active material according to any one of the preceding claims, characterized in that the sulfur-containing material and the carbon nanofillers represent. from 20% to 100% by weight relative to the total weight of the active ingredient. 17. Active material according to any one of the preceding claims, characterized in that it is in the form of a powder, comprising particles having a mean size of less than 150 gm, a median diameter d 50 of between 10 and 60 gm and a diameter. median d90 less than 100 pm 18. Use of the active ingredient according to any one of the preceding claims in an electrode.
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    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 3 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 4 |
    2018-11-20| PLFP| Fee payment|Year of fee payment: 5 |
    2019-11-14| PLFP| Fee payment|Year of fee payment: 6 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 7 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463052|2014-12-22|
    FR1463052A|FR3030890B1|2014-12-22|2014-12-22|ACTIVE ELECTRODE MATERIAL FOR BATTERY LI / S|FR1463052A| FR3030890B1|2014-12-22|2014-12-22|ACTIVE ELECTRODE MATERIAL FOR BATTERY LI / S|
    EP15828749.0A| EP3238295B1|2014-12-22|2015-12-21|Active electrode material for a li-s battery|
    PCT/FR2015/053682| WO2016102865A1|2014-12-22|2015-12-21|Active electrode material for a li-s battery|
    PL15828749T| PL3238295T3|2014-12-22|2015-12-21|Active electrode material for a li-s battery|
    HUE15828749A| HUE046899T2|2014-12-22|2015-12-21|Active electrode material for a li-s battery|
    JP2017533420A| JP6979356B2|2014-12-22|2015-12-21|Active electrode material for Li-S batteries|
    MX2017008034A| MX2017008034A|2014-12-22|2015-12-21|Active electrode material for a li-s battery.|
    KR1020177019765A| KR102002715B1|2014-12-22|2015-12-21|Active electrode material for a li-s battery|
    CN201580070971.6A| CN107112508B|2014-12-22|2015-12-21|Active electrode material for LI-S batteries|
    CA2969185A| CA2969185A1|2014-12-22|2015-12-21|Active electrode material for a li-s battery|
    SG11201705117TA| SG11201705117TA|2014-12-22|2015-12-21|Active electrode material for a li-s battery|
    US15/538,030| US10446831B2|2014-12-22|2015-12-21|Active electrode material for a Li—S battery|
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