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    • 专利摘要:
    Porous membrane comprising a first main surface (1) and a second main surface (2) separated by a thickness (3) in which: - carbon nanotubes (4), defining through pores or channels open at their two ends (5 ,6), with a diameter less than or equal to 100 nm, oriented in the direction of the thickness (3) of the membrane and all substantially parallel, over the entire thickness (3) of the membrane, connect the first main surface (1) and second main surface (2); - the carbon nanotubes are separated by a space, and said space between the carbon nanotubes is completely filled with at least one solid material. This porous membrane can be a filtration membrane. Alternatively, this porous membrane may be an electrolyte membrane, particularly for electrochemical devices. Process for the preparation of this membrane. Electrochemical device, such as a lithium battery comprising said electrolyte membrane.
    公开号:FR3034258A1
    申请号:FR1552572
    申请日:2015-03-26
    公开日:2016-09-30
    发明作者:Jean-Marc Zanotti；Quentin Berrod；Jean Dijon；Filippo Ferdeghini；Patrick Judeinstein
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] POROUS MEMBRANE, ESPECIALLY ELECTROLYTE MEMBRANE OR FILTRATION MEMBRANE, ITS PREPARATION METHOD, AND ELECTROCHEMICAL DEVICES COMPRISING THE SAME. TECHNICAL FIELD The invention relates to a porous membrane.
    [0002] This porous membrane may be a filtration membrane. Or, this porous membrane may be an electrolyte membrane, particularly for electrochemical devices. In particular, the invention relates to an ionic liquid electrolyte membrane or a polymer electrolyte membrane for electrochemical devices.
    [0003] The invention further relates to a method for preparing said membrane. The invention also relates to an electrochemical device comprising this electrolyte membrane, in particular an ionic liquid electrolyte or a solid polymer electrolyte electrolyte. This electrochemical device may be, in particular, an alkaline metal accumulator. In particular, the invention relates to a lithium battery, in particular a lithium metal battery or a lithium-ion battery, comprising said electrolyte membrane. The technical field of the invention can be defined as that of electrochemical devices, in particular that of lithium accumulators and more precisely that of lithium-metal accumulators and / or lithium-ion accumulators comprising an electrolyte. Such accumulators are used in particular in electronic devices and hybrid or electric vehicles. STATE OF THE PRIOR ART Accumulators used in hybrid or electric vehicles must be able to both store a large quantity of energy and supply it in a short time. Compared to other electrochemical energy storage systems, lithium batteries offer very high energy densities, generally of the order of 150 Wh / kg, but still modest powers (1-3 kW / kg), in particular because of kinetic factors and / or limitation of the transport of charge carriers within the electrolyte. The electrolyte may be in particular a proton or proton conductor transporter such as Nafion®, a protonic ionic liquid or an acid dissolved in a polymer, a pure ionic liquid, an ionic liquid containing an ionically conductive salt such as a salt alkaline, a liquid organic solvent or an organic polymer containing an ionic conductive salt, or a combination of several electrolytes which have just been listed. The electrolytes used in these accumulators may in particular comprise salts dissolved in a liquid or solid medium, such as a polymer, which makes it possible to dissociate these salts into charged species. For example, the electrolytes of lithium metal or lithium-ion batteries may consist of lithium salts dissolved in a polymer matrix, hence the name "polymer electrolyte" or "polymer electrolyte". This is called a "lithium-polymer" accumulator.
    [0004] The usual polymers of these polymeric electrolytes are semi-crystalline polymers in which amorphous and crystalline phases coexist, or amorphous polymers or crosslinked polymers. Thus, the polymer matrix of lithium-metal accumulators is generally composed of polymers based on polyethylene oxide or POE ("PEO" in English), corresponding to the formula [CH2-CH2-O] where the value of n is, for example, about 3000. In the following, the term "solvent" is generally used to mean the liquid or solid medium, and the medium consisting of the charged species and the "electrolyte" will generally be referred to as "electrolyte". solvent. In addition, to ensure and ensure the safety of the electrochemical system, such as an accumulator or a battery, for example to prevent its ignition or leakage of chemical species into the environment, it is important to ensure good mechanical strength of the envelope of the electrochemical system and the electrolyte and thus uses a porous matrix or a membrane to trap the electrolyte. The terms electrolyte membrane are then used.
    [0005] The conductivity of the electrolytes is the product of the charge carrier concentration by their mobility. The mobility is proportional to the diffusion coefficient of the charge carriers and therefore inversely proportional to the viscosity of the solvent. Consequently, it appears that the power of the electrochemical devices such as the accumulators is controlled essentially by the viscosity of the electrolyte and the concentration of charge carriers, and so we constantly try to reduce the viscosity of the electrolyte and to increase the concentration of charge carriers. To increase the concentration of charge carriers, it is necessary to use a solvent in which the salt is soluble and dissociated.
    [0006] The usual solutions for decreasing the viscosity of the electrolyte are increasing the temperature at which the electrochemical system, such as an accumulator, or the addition of plasticizer additives in the polymer when the electrolyte is an electrolyte. solid polymer. For automotive applications, for example, if the electrolyte is an electrolyte polymer, the accumulator should be maintained at about 80 ° C. This constraint is very unfavorable from the point of view of overall energy efficiency, limits the field of use of accumulators comprising such electrolytes to heavy equipment such as motor vehicles and prohibits any application in the field of "consumer" electronics and especially in computers, 25 MP3 players and all light and portable electronic devices. The incorporation of plasticizers in the polymer increases the amorphous phase fraction of the polymer and thus increases the ionic conductivity, but it only achieves a conductivity that is still too low. FR-A1-2 963 481 [1] relates to an electrolyte mineral membrane in which: the membrane is a porous membrane made of an electrically insulating metal or metalloid oxide comprising a first main surface (1 ) and a second main surface (2) separated by a thickness (3); pores or through-channels (4) open at both ends (5, 6), of a diameter less than or equal to 100 nm, oriented in the direction of the thickness (3) of the membrane and all substantially parallel, over the entire thickness (3) of the membrane, connect the first main surface (1) and the second main surface (2); and an electrolyte is confined in the pores (4) of the membrane.
    [0007] In this membrane, the pores or channels are created by chemical etching in the substrate, for example by anodizing an aluminum plate with oxalic acid and then dissolving the oxide with a mixture of chromic acid and 'Phosphoric acid. This membrane still has insufficient ionic conductivity of the electrolyte, and is fragile and brittle as it is not ductile. It is also difficult to implement by extrusion processes. There is therefore, in view of the foregoing, a need for an electrolyte membrane, intended in particular for use in a lithium accumulator, such as a lithium-metal or lithium-ion accumulator, which makes it possible to improve the performance of existing electrolyte membranes. There is, in particular, a need for an electrolyte membrane, which has a high ionic conductivity, and improved at ambient temperature, for example up to 10-1 S / cm, without addition of plasticizing additives to The electrolyte. The purpose of the present invention is in particular to provide an electrolyte membrane, which meets these needs, among others. The object of the present invention is still to provide an electrolyte membrane which does not have the drawbacks, defects, limitations and disadvantages of the electrolyte membranes of the prior art and which solves the problems of the electrolyte membranes of the art. prior. In particular, the object of the present invention is to provide an electrolyte membrane which has improved performance, particularly with respect to insufficient ionic conductivity at ambient temperature, without the need to add additives such as plasticizer additives, with the electrolyte. The object of the present invention is consequently to provide an electrolyte membrane which, when it is used in an accumulator, provides a significant gain in the power delivered by these accumulators with respect to the accumulators which use the membranes. of the prior art. SUMMARY OF THE INVENTION This and other objects are achieved in accordance with the invention by a porous membrane comprising a first major surface (1) and a second major surface (2) separated by a thickness (3). ) in which: carbon nanotubes (4), defining pores or open channels at both ends (5, 6), with a diameter of less than or equal to 100 nm, oriented in the direction of the thickness ( 3) of the membrane and all substantially parallel, over the entire thickness (3) of the membrane, connect the first main surface (1) and the second main surface (2); the carbon nanotubes are separated by a space, and said space between the carbon nanotubes is completely filled with at least one solid material. Advantageously, an electrolyte is confined inside the carbon nanotubes.
    [0008] In this case, the membrane is called an electrolyte membrane. Indeed, it should be noted that the term "electrolyte membrane" generally refers to the membrane in which the electrolyte is confined within the carbon nanotubes, while "membrane" refers only to the membrane as such without electrolyte confined within the carbon nanotubes.
    [0009] The membrane, as such, may in particular be used to filter a fluid such as a liquid, which is then circulated in the pores from the first main surface (1) to the second main surface (2). ) or vice versa. The membrane can then be called "filtration membrane".
    [0010] By room temperature is generally meant a temperature of 15 ° C to 30 ° C, for example 20 ° C to 25 ° C. Advantageously, the first and second major surfaces are flat and parallel, the membrane is a planar membrane, and the nanotubes, pores or channels, are substantially aligned, or aligned, perpendicular to said surface.
    [0011] As already mentioned above, the pores are open pores, opening at both ends. These two ends are located respectively at least at the first and second major surfaces. In other words, these two ends can not be located below the level of the first or second major surface, within the membrane. These two ends may be located respectively at the first and second major surfaces. Either one of these two ends or these two ends may be situated respectively beyond the first and second major surfaces, that is to say that the nanotubes exceed, go beyond, this first surface. main and / or second main surface (this is the case in the accompanying figures). There is virtually no limitation on carbon nanotubes. However, the pores or channels, in other words the core of the nanotubes must not be obstructed, in particular by catalyst residues, for example ferrocene, or by structural defects of the wall of the nanotubes. In other words, the channels or pores must be through, between the first main surface of the membrane and the second main surface of the membrane and also not be obstructed, so that the fluid, such as the electrolyte or the fluid, such as A liquid to be filtered flows freely in these channels or pores between the first major surface of the membrane and the second major surface of the membrane.
    [0012] The carbon nanotubes may be chosen from single-wall carbon nanotubes and multi-wall carbon nanotubes. Carbon nanotubes are electronic conductors which may limit their use in applications where they must instead be electronic insulators, for example when they are to be used as a battery separator element. To make them electrically insulating, carbon nanotubes can be functionalized on their outer wall (wall opposite to pores, channels) in the case of single-wall carbon nanotubes, or on their outermost wall in the case of multiwall carbon nanotubes. .
    [0013] Thus, the carbon nanotubes can be functionalized for example by fluorination, or by means of an organic compound which makes them electronic insulators such as aryl diazonium. In this respect reference may be made to FR-A1-2 896 716. On the other hand, carbon nanotubes, since they are electronically conductive, may be used as an electrode. However, to increase their performance, the carbon nanotubes may also be functionalised on their outer wall, for example by redox species, such as anthraquinones, and / or electroactive species, such as ferrocenepyrene. Advantageously, the carbon nanotubes have an internal diameter of 1 to 100 nm, preferably 1 to 20 nm, more preferably 1 to 3 nm. By substantially parallel in the sense of the invention, it is generally understood that the carbon nanotubes, and the pores or channels, have an orientation mosaicity that does not exceed 10%. Advantageously, the carbon nanotubes and the pores or channels have a length, which generally corresponds to the thickness of the membrane, from 10 microns to 100 mm, preferably from 50 microns to 500 microns, for example 150 microns. Advantageously, the carbon nanotubes, and the channels or pores are arranged in a regular pattern, for example in rows or in a matrix, for example according to a compact hexagonal matrix.
    [0014] More precisely, when the membrane is observed, it is the ends, apertures opening out from these carbon nanotubes and channels or pores, for example at each of the first main surface and the second main surface, which are arranged in a manner a regular pattern on the first main surface and / or the second major surface (see Figure 1). Advantageously, the carbon nanotubes are separated by a distance of the order of magnitude of the external diameter, dext, carbon nanotubes), for example by a distance of 1 to 100 nm, preferably from 1 to 20 nm, preferably still 1 to 3 nm. It should be pointed out that the outer diameter of a nano-walled multi-walled carbon nanotube of n inner diameter is dex = +2 x n x 0.34 nm. The solid material is chosen in particular according to the intended use of the membrane. Thus, in the case where the membrane is an electrolyte membrane, then the solid material may be selected from electronic insulating materials or from electronic conductive materials whose outer surface, in contact with the outside of the membrane, has been made electronically insulating. In the case where the membrane is a filtration membrane, then the solid material can be both electronically conductive, as a metal, and electronically insulating.
    [0015] Advantageously, the solid material may be chosen from organic polymers such as polystyrene; metals, and metal oxides. The electrolyte may be, for example, a proton or proton conductor such as a protonic ionic liquid or a proton conductive polymer such as Nafion®, a zwitterionic ionic liquid, an acid dissolved in an organic polymer, an ionic liquid ( pure), an ionic liquid containing an ionic conductive salt such as an alkali metal salt or an alkaline earth metal salt, a liquid organic solvent or an organic polymer containing an ionically conductive salt such as a salt of alkali metal or alkaline earth metal, an ionic liquid in an organic polymer, a mixture of an organic polymer and an organic solvent, a mixture of an ionic liquid and an organic solvent, a mixture of an ionic liquid , an organic solvent 3034258 9 and an alkali or alkaline earth metal salt, a mixture of an organic polymer, an organic solvent and an alkali or alkaline earth metal salt , a mixture of a salt of an alkali or alkaline earth metal, for example lithium in a protic ionic liquid; or a combination of several electrolytes which have just been listed. It should be noted that generally the electrolyte contains an ionically conductive salt, except for example if the electrolyte comprises a protic ionic liquid. Ionic liquids, protonic ionic liquids, and zwitterionic ionic liquids designate three families of different compounds.
    [0016] Ionic liquids can generally be defined as liquid salts comprising a cation and an anion. Ionic liquids are thus generally composed of an organic cation, giving them a positive charge, which is associated with an anion which gives them a negative charge. In addition, the ionic liquids are, as their name indicates, generally liquid in the temperature range 0 ° C to 200 ° C, in particular 0 ° C to 100 ° C, especially around the ambient temperature, and so they are often referred to as "RTIL" (or "Room Temperature Ionic Liquids" in English). The diversity of ionic liquids is great. Thus, can the C + cation of the ionic liquid be chosen from hydroxonium, oxonium, ammonium, amidinium, phosphonium, uronium, thiouronium, guanidinium, sulfonium, phospholium, phosphorolium, iodonium or carbonium cations; and heterocyclic cations such as pyridinium, quinolinium, isoquinolinium, imidazolium, pyrazolium, imidazolinium, triazolium, pyridazinium, pyrimidinium, pyrrolidinium, thiazolium, oxazolium, pyrazinium, piperazinium, piperidinium, pyrrolium, pyrizinium, indolium, quinoxalinium, thiomorpholinium, morpholinium cations. and indolinium; and tautomeric forms thereof. The anion of the ionic liquid may be selected from halides such as Cl-, among more complex anions such as BF4, B (CN) 4, CH3BF3-, CH2CHBF3-, CF3BF3-, m-CnF2,113F3 where n is a integer such as 1 n 10, PF6, CF3CO2, CF3SO3, N (SO2CF3) 2, N (COCF3) (SOCF3), N (CN) 2-, C (CN) 3-, SCN-, SeCN-, CuCl2-, AlC14 -, AsF6 -, CIO4, BOB -, ODBF-, B (C6I-16) -, RFS03-, N (C2F6SO2) 2-, C (RFSO2) 3- wherein RF is selected from a fluorine atom and a perfluoroalkyl group comprising from 1 to 9, preferably from 1 to 8 carbon atoms, especially a - (CF 2) nCF 3 group where n is an integer from 1 to 8, TFSI is the acronym for bis (trifluoromethylsulfonyl) imide, BOB that of bis (oxalato) borate, and BETI that of bis (perfluoroethylsulfonyl) imide.
    [0017] Examples of ionic liquids are given in FR-A-2 935 547 to the description of which reference may be made. The electrolyte may comprise at least one organic polymer. The organic polymer may be chosen in particular from crystalline or semi-crystalline organic polymers before confinement in the carbon nanotubes.
    [0018] By crystalline or semi-crystalline organic polymer (before confinement) is generally meant that said organic polymer is crystalline or semi-crystalline for any temperature below 100 ° C, and especially at room temperature. However, the organic polymer may also be chosen from liquid or amorphous polymers (before confinement) or from crosslinked polymers. The liquid or amorphous polymers at a temperature below 100 ° C., for example at room temperature, are preferably chosen from polymers, especially oligomers, of POE, and their derivatives. When the electrolyte comprises an organic polymer that is crystalline, semi-crystalline, liquid or amorphous, the electrolyte generally further comprises an ionically conductive salt, and the electrolyte is then generally referred to as a polymer electrolyte or an electrolyte polymer. The electrolyte, before it is confined, before confinement, in the carbon nanotubes, is also called unconfined electrolyte, electrolyte before confinement, and it is often referred to as the electrolyte "by volume" or bulk electrolyte.
    [0019] Thus, if the electrolyte comprises or consists of an organic polymer, the polymer, before it is confined, also called non-confined polymer, is often referred to as "bulk" or "bulk" polymer. ". By polymer within the meaning of the invention is meant homopolymers as well as copolymers as oligomers.
    [0020] Advantageously, the organic polymer that is semi-crystalline or crystalline, or liquid or amorphous, is chosen from polymers that allow good solvation of alkali metal ions, such as Li, or alkaline earth metal ions. . Advantageously, the organic polymer, in particular semi-crystalline or crystalline, is chosen from homopolymers and copolymers of ethylene oxide and their derivatives. Homopolymers and copolymers of ethylene oxide and their semicrystalline or crystalline derivatives generally have a crystallinity of at least 10%. Advantageously, the organic polymer has a molar mass of less than 106 g / mol, preferably less than 105 g / mol.
    [0021] It is evident that the molar mass of the organic polymer is at least equal to the molar mass of the monomer (s) used to prepare it. This molar mass is, for example, from 105 to 44 g / mol in the case of POE. This is one of the additional advantages of the membrane according to the invention to allow the use in the electrolyte of polymers of lower molecular weight, and therefore less viscous, more fluid than the polymers hitherto used in the electrolytes. Indeed, in the membrane according to the invention, an excellent confinement of the polymer of the electrolyte in the channels, pores defined by the nanotubes, is obtained, and this even for polymers of lower molar mass, and therefore less viscous, more fluid . There is therefore no dispersion of the electrolyte in the environment during an incident even if the polymer of the electrolyte is a polymer of low molar mass, "flowing", because the electrolyte does not leave the channels, pores, do not escape. In the membranes of the prior art, the confinement of the electrolyte in the pores being less well ensured, it is necessary to use a high molecular weight polymer, viscous which does not run, so that it does not escape not and does not disperse in the environment during an incident. Advantageously, the organic polymer has a molar mass less than its critical entanglement mass. The critical entanglement mass is generally defined as the mass from which the polymer dynamics is in a creep regime.
    [0022] For example, the critical entanglement mass of POE is 3600 g / mol.
    [0023] Advantageously, the polymer is chosen from poly (ethylene oxide) s having a molecular mass of less than 3600 g / mol, preferably 44 (mass of the monomer) at 2000 g / mol. The ionic conductive salt may be an alkali metal salt or a salt of an alkaline earth metal. The salt of an alkali metal may be for example a lithium salt or a sodium salt, and the salt of an alkaline earth metal may be for example a magnesium salt. The lithium salt may be chosen for example from LiAsFs, LiClO 4, LiBF 4, LiPF 6, LiBOB, LiODBF, LiB (C 61-15), LiRFSO 3, for example LiCF 3 SO 3, LiCH 3 SO 3, LIN (RFSO 2) 2, for example LiN (CF 3 SO 2) 2 ( LITFSI) or LiN (C2F5SO2) 2 (LiBETI), LIC (RFS02) 3, for example LiC (CF3SO2) 3 (LiTFSM), in which RF is selected from a fluorine atom and a perfluoroalkyl group comprising from 1 to 9 carbon atoms. carbon, LiTFSI is the acronym for lithium bis (trifluoromethylsulfonyl) imide, LiBOB that of lithium bis (oxalato) borate, and LiBETI that of lithium bis (perfluoroethylsulfonyl) imide.
    [0024] The sodium salt may be selected from the salts analogous to the lithium salts already listed above but comprising a sodium ion instead of a lithium ion. Advantageously, the ionic conductive salt concentration such as an alkali metal salt or a salt of an alkaline earth metal, when it is present in the electrolyte, and in particular in the polymer electrolyte, may be from 1 to 50% by weight relative to the mass of the electrolyte, for example the polymer electrolyte. Advantageously, the electrolyte is a polymer electrolyte which comprises a poly (ethylene oxide), preferably a semi-crystalline poly (ethylene oxide) (before confinement) and a lithium salt, preferably LiTFSI. Advantageously, the ratio of lithium atoms to oxygen atoms of the polyethylene glycol ether groups is less than or equal to 1/8, for example this ratio may be 1/8, 1/12 or 1/16. Alternatively, the electrolyte may comprise, preferably, an organic solvent containing an ionically conductive salt.
    [0025] Alternatively, the electrolyte may comprise, preferably, a proton conductor (carrier), for example a sulfonated polymer such as Nafion®. Advantageously, the electrolyte, such as a polymer electrolyte, completely fills the nanotubes and the pores or channels. It should be noted that the electrolyte, such as a polymer electrolyte is not in the form of particles, in particular discrete nanoparticles but in the form of a compact and continuous mass filling each carbon nanotubes, pores and in contact with the walls thereof.
    [0026] The membrane according to the invention, in particular the electrolyte membrane, for example a polymer electrolyte membrane according to the invention, has never been described in the prior art as represented in particular by document [1]. The electrolyte membrane, for example a polymer electrolyte membrane according to the invention, does not exhibit the defects of the electrolytes, for example the polymer electrolytes of the prior art, and provides a solution to the problems posed by the electrolytes, for example the polymer electrolytes. of the prior art. The porous electrolyte membrane according to the invention has at least three essential characteristics, namely on the one hand the presence of pores of nanometric section (defined by the carbon nanotubes), which confine an electrolyte, for example a polymer electrolyte or an ionic liquid; then, the fact that these pores are through pores substantially oriented in the same direction, or even oriented in the same direction, namely the direction of the thickness of the membrane and all substantially parallel or parallel; and finally the fact that the pores or channels are specifically pores defined by means of carbon nanotubes.
    [0027] More specifically, the pores or channels are defined by the carbon nanotubes, or more exactly by the inner, inner wall, of the carbon nanotubes. As a result, these pores or channels have a smooth surface, in contrast to pores or channels that are not defined by carbon nanotubes, for example channels or pores that are created in a mineral substrate by etching as in document [ 1].
    [0028] By smooth surface, it is generally understood that the surface does not have irregularities (asperities, reliefs, etc.) at the subnanometric scale, that the surface does not cause chemical and / or physico-chemical interactions such as friction with the fluid confined in the channels.
    [0029] The flow of a fluid such as an electrolyte into the channels defined by the carbon nanotubes of the membrane according to the invention occurs at a non-zero speed at the wall due to the absence of interactions between the fluid. and the wall, and in particular thanks to the absence of friction. In document [1], the membrane channels are defined in a metal oxide or metalloid, and thus there are strong interactions between the fluid in the channels, such as an electrolyte and the walls of the channels. Channels that are irregular and rough. These interactions are reduced or even eliminated in the channels of the membrane according to the invention defined by carbon nanotubes. In addition, as noted above, the channels should not be obstructed, but the absence of obstruction in the channels should not be confused with the absence of interactions between the fluid and the wall. The combination of these three characteristics has never been described in the prior art and clearly differentiates the membrane according to the invention membranes according to the prior art. In particular, an electrolyte membrane having pores defined by carbon nanotubes has never been described. In other words according to the invention, an electrolyte is confined in a membrane having both a nanometric porosity and a macroscopic orientation which are created specifically by carbon nanotubes. The membrane according to the invention achieves the aforementioned aims and provides a solution to the problems mentioned above. It can be said that the membrane according to the invention exploits the so-called unidimensional nanoscale (1D) confinement effect of an electrolyte within the membrane, more exactly in pores or channels defined by carbon nanotubes (FIG. to increase the conductivity of the electrolyte and to triple or even increase the power of 10 electrochemical energy storage devices comprising said membrane.
    [0030] The combination of the three characteristics listed above gives the membrane according to the invention, in particular to the electrolyte membrane according to the invention, for example polymer electrolyte or ionic liquid, advantageous and surprising properties especially as to its conductivity. ionic, especially at room temperature. Thus, thanks to the membrane according to the invention, a gain of a factor of 3 or even a factor of 10 is obtained on the transport properties and therefore on the ionic conductivity. Compared to an electrolyte in volume, "bulk", unconfined, we show here a gain of a factor 3 on the diffusion coefficient of an ionic liquid (see examples).
    [0031] As a consequence, the membrane according to the invention allows a significant gain in the power delivered by the accumulators comprising it. The membrane according to the invention therefore contributes to filling the power / energy gap existing in the performance of low carbon energy storage systems. It can be said that the electrolyte membrane, for example the polymer electrolyte or the ionic liquid electrolyte according to the invention, because of the three essential characteristics mentioned above, makes it possible to improve the performance of the electrolytes, and in particular electrolytic or liquid polymers. Ionic room temperature through the setting in conjunction, combination of at least three effects. In other words, it can be considered that the improvement in the performance of the electrolyte and in particular the gain in conductivity, has its origin on the molecular scale-that is to say a few Angstroms-in the combination, combination at least three of the following effects: i) the extreme confinement of the electrolyte molecules, for example of ionic liquid, polymer and possibly ionic salt, within the channels or pores defined by the carbon nanotubes NTCs, in other words in the soul of the NTCs, induces a frustration of the spontaneous organization which the electrolyte normally possesses when it is in volume. In the case of ionic liquids, for example, it frustrates, counteracts, forces the organization into self-organizing transient clusters of nanometric size.
    [0032] This confinement is due to the nanometric diameter of the nanotubes, which generally have an internal diameter of 1 to 100 nm, preferably of 1 to 20 nm, more preferably of 1 to 3 nm. It is believed that the increase in diffusion coefficient and / or ionic conductivity is inversely proportional to the diameter of the CNTs. The maximum increase in diffusion coefficient and / or ionic conductivity is obtained using NTCs whose diameter is in the range of 1 to 3 nm. ii) the incommensurability of the structure of the molecules of the electrolyte with the "smooth" internal surface of the NTCs induces a sliding phenomenon on this wall, because the coefficient of friction at the NTC / electrolyte interface is zero. iii) the macroscopic orientation of the CNT pores imposes a preferred direction, and without tortuosity, the transport of the electrolyte from one electrode to another. In addition, in the membrane according to the invention, there is a transfer to the membrane of the stress of mechanical strength of the electrolyte, which allows the use of liquid or low molecular weight electrolytes, for example oligomers and thus significantly improve the conductivity of the electrolyte. In addition, nanoconfinement, generally defined by a diameter of the NTCs and pores of the membrane which confine the electrolyte less than 100 nm, for example 10-50 nm, makes it possible, particularly in the case of polymer electrolytes, to reduce the melting point of the polymer by the Gibbs-Thomson effect, so that the melting of the polymer preferably takes place at room temperature More generally, in the case of compounds of the electrolyte which comprises a crystalline fraction, in other words crystalline or semi-crystalline compounds, the nanoconfinement has the effect of reducing, or even totally eliminating the crystalline fraction that said compound has before its incorporation into the pores or channels of the membrane, and thus to increase the conductivity. It can be said that the nanoconfinement leads to a partial or total amorphization of the compound and a system with greater mobility.
    [0033] In the case of a semi-crystalline polymer, such as POE, the nanoconfinement will lead to partial amorphization and advantageously to a decrease in the melting temperature of the polymer. In the liquid state, above its melting point, the polymer is generally 10 to 100,000 times less viscous than below its melting point. One-dimensional conduction in pores with low tortuosity means that the electrolyte transport properties of one electrode to another are not affected in the membrane according to the invention. In the case where the compound is already liquid or amorphous at a temperature below 100 ° C., and especially at ambient temperature, it is this unidirectional 1D aspect which is predominant with respect to the nanocontainment aspect. In conclusion, with respect to the electrolytes, and in particular to the ionic polymer or ionic electrolytes of the prior art, the advantages provided by the membrane according to the invention are essentially in terms of performance, safety and economic viability. . As regards performance, the membrane according to the invention has the advantages of having an operating temperature generally around ambient temperature and of having a quasi-one-dimensional conduction with increased conductivity.
    [0034] With regard to safety, the membrane according to the invention has the advantages of ensuring confinement of the electrolyte and of preventing the electrolyte from being released into the environment in the event of rupture of the accumulator. which is particularly advantageous in the case of liquid electrolytes and to limit the phenomenon of dendritic growth and therefore the risk of spontaneous ignition of the accumulator.
    [0035] With regard to the economic viability, the membrane according to the invention has the advantage of allowing a reduction in the quantity of conductive salt possibly entering the composition of the electrolyte, in particular lithium salt, which leads to a decrease in the cost of the electrolyte and the accumulator containing it. In addition, since the dendritic growth phenomenon and the associated risks are limited, the electrolyte membrane, for example the polymer electrolyte membrane according to the invention, can have its applications extended to portable and / or "general public" electronics. . The invention furthermore relates to a method for preparing the electrolyte membrane according to the invention, as described above, in which the following successive steps a) and b) are carried out: a) growing carbon nanotubes, all substantially parallel, and spaced apart, on a surface of a substrate provided with a carbon nanotube growth catalyst; b) said space between the carbon nanotubes is completely filled with a solid material; or else the following step a1) is carried out: a1) carbon nanotubes, all of which are substantially parallel, are grown and separated on a surface of a substrate and inside the pores of a porous solid material with oriented pores ; Then, at the end of step b) or of step a1), the following step c) is carried out: c) the substrate is eliminated, any excess solid material in excess, and the two ends are opened. carbon nanotubes. Advantageously, after step c), the interior of the nanotubes is filled with an electrolyte. It can be said that during step a), a forest of carbon nanotubes or a carpet of carbon nanotubes is grown on the substrate. Advantageously, the growth substrate may be a silicon wafer, or a strip of stainless steel or aluminum on which is deposited a layer of alumina, and the growth catalyst of carbon nanotubes is deposited on the alumina layer. Advantageously, the growth catalyst of carbon nanotubes may be chosen from iron, nickel, cobalt, and their alloys. Advantageously, the carbon nanotubes can be grown by a CVD chemical vapor deposition process.
    [0036] The solid material may be an organic polymer, and then step b) is carried out either by dissolving the organic polymer in a solvent to form a solution of the organic polymer, completely filling the space between the carbon nanotubes with the solution of the organic polymer and evaporating the solvent. Either by heating the organic polymer in the absence of solvent above its glass transition temperature (Tg) or melting point to make it fluid, and allowing the fluid polymer to absorb in the space between carbon nanotubes. either filling the gap between the carbon nanotubes with a mixture comprising organic monomers (such as styrene, methyl methacrylate, or the like), or organic oligomers modified with reactive functions, or organic copolymers, and in addition one or more photosensitive and / or thermally sensitive free radical initiator (s); and then crosslinking said mixture thermally or by means of photon radiation.
    [0037] Alternatively, the solid material may be a metal, and then step b) is performed by depositing said metal by an electrochemical deposition process in the space between the carbon nanotubes. Or, the solid material may be a metal oxide and then step b) is performed by depositing said metal oxide by an electrochemical deposition process, or by a sol-gel process, in the space between the nanotubes of carbon. Whatever the solid material, step b) can also be performed by vacuum projecting said solid material in the space between the carbon nanotubes (vacuum sputtering).
    [0038] To fill the interpore space of the CNTs and to make a membrane, an interesting metal would undoubtedly be aluminum which is light and fairly ductile. It could be deposited by electrodeposition and then (in the case where the membrane is intended to be used as a separator) perform a simple short anodization to transform the outer surfaces into alumina, which is an insulating material. Thus, finally, inside the membrane, there is then metal but the outer surfaces of the membrane in contact with the electrodes are insulating. Advantageously, step c) can be performed by mechanical polishing and / or plasma etching.
    [0039] The invention further relates to an electrochemical device comprising an electrolyte membrane according to the invention, for example a polymer electrolyte as described above. In particular, the invention relates to a lithium battery comprising an electrolyte membrane, as described above, a positive electrode, and a negative electrode (Figures 2, 3 and 4). This lithium battery may be a Li-Metal battery in which the negative electrode is made of lithium metal or this lithium battery may be a lithium-ion battery. Such a device has all the advantages inherently associated with the implementation in such devices of the electrolyte membrane according to the invention. The invention also relates to the use of the membrane according to the invention for filtering a stream of a fluid, in particular a stream of a liquid. The invention will now be described more specifically in the description which follows, given by way of illustration and not limitation with reference to the accompanying drawings.
    [0040] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic representation of steps a) (FIG. 1A), b) (FIG. 1B) and c) (FIG. 1C) of the process according to the invention during which a carpet or forest of carbon nanotubes (FIG. 1A ) is transformed into a membrane of carbon nanotubes (Figure 1C). - Figure 2 is a schematic view of an accumulator, such as a lithium battery comprising the electrolyte membrane according to the invention. Figure 3 is a schematic view of a particular embodiment of a lithium battery comprising the electrolyte membrane according to the invention.
    [0041] FIG. 4 is a schematic view of another particular embodiment of a lithium accumulator, called a "full 1D" lithium accumulator, comprising the electrolyte membrane according to the invention. Figure 5 is a scanning electron micrograph of the carbon nanotube mat or forest obtained at the end of step 1 of Example 1. The scale shown in Figure 5 represents 10 μm. FIG. 6 is a photograph taken by scanning electron microscope of the membrane obtained at the end of step 3 of example 1. The scale shown in FIG. 6 represents 100 μm. FIG. 7 is a graph which gives, at room temperature, the self-diffusion coefficient, measured by 19 F NMR, of the ionic liquid confined in the pores of the NTC membrane of Example 1, to namely 1-octyl-3-methylimidazolium tetrafluro-borate, (OMIMBF4) (points A); and the self-diffusion coefficient of this same ionic liquid, namely 1-octyl-3-methylimidazolium tetrafluoroborate, (OMIMBF4), but not confined in the pores of the membrane (o-points). This non-confined ionic liquid is also called ionic liquid "volume" or "bulk" ("bulk"). On the abscissa is the diffusion function (-G 2 1262 (A_6 / 3)) in s / cm2 (second / cm2), where G is the pulsed field gradient, y the gyromagnetic ratio of the studied nucleus - here the fluorine-19- 6 the duration of the gradient pulse, and A diffusion time (in this experiment we used a stimulated gradient-type sequence with 6 = 3 ms, A = 50 ms and G varying from 5 G / cm to 700 G / cm). The ordinate is the relative evolution of the NMR signal (without unit). FIG. 8 is a block diagram of the device which made it possible to measure by impedance spectroscopy, at ambient temperature, the conductivity of the ionic liquid confined in the pores of the NTC membrane of Example 1, namely the 1-octyl-3-methylimidazolium tetrafluoroborate, (OMIMBF4); and the conductivity of this same ionic liquid, namely 1-octyl-3-methylimidazolium tetrafluoroborate, (OMIMBF4), but not confined in the pores of the membrane.
    [0042] Figure 9 is a graph which gives the electrical impedance of the ionic liquid confined in the membrane pores of NTCs of Example 1, namely 1-octyl-3-methylimidazolium tetrafluoroborate, (OMIMBF4) ("OmimBF4). Bulk + CNT "); and the impedance of this same ionic liquid, namely 1-octyl-3-methylimidazolium tetrafluoroborate, (OM1MBF4), but not confined in the pores of the membrane ("OmimBF4 Bulk"). On the ordinate is carried the imaginary part of the electrical impedance (in Ohm), and in abscissa is carried the real part of the electrical impedance (in Ohm).
    [0043] DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS This description refers more particularly to an embodiment in which the porous membrane according to the invention is an electrolyte membrane, in particular an ionic liquid electrolyte membrane, in particular the electrolyte membrane of the invention. a lithium battery, but it is obvious that the description which follows may easily be extended, if necessary, to any porous membrane, in particular to any electrolyte membrane which may be implemented in any electrochemical device or system, that is the electrolyte, but also to the filtration membranes. In addition, the following description is rather made for convenience in connection with the method of preparing the membrane according to the invention but it also contains teachings relating to the membrane prepared by this method. To prepare the membrane according to the invention, it is possible to start by preparing, synthesizing, a carpet of carbon nanotubes, which can also be described as a forest of carbon nanotubes, on a surface (3) of a solid substrate. (4) (Fig.
    [0044] 1A).
    [0045] From this carpet, or forest, a membrane is then obtained by filling, filling the inter-tube space and opening the carbon nanotubes on each side of the membrane (see FIG.
    [0046] 1B and FIG.
    [0047] 1 C). The NTCs mat (1) can be synthesized by a CVD chemical vapor deposition process.
    [0048] According to a first embodiment, a multi-walled nanotube mat (1) can be synthesized on a surface (3) of a solid substrate (4). In this case, the growth substrate is a silicon wafer on which is deposited by an ALD process ("Atomic Layer Deposition") a layer of alumina 5 generally 20 nm thick. According to one variant, this alumina layer can be deposited on the substrate by sputtering, or by an ion beam sputtering (IBS) method. On this substrate a catalyst is deposited, this catalyst can be for example iron, nickel, cobalt, or an alloy of these metals. This catalyst is generally in the form of a layer, for example of a thickness of 0.2 to 2 nm. In this embodiment, in which a carpet of small particles (ie with a diameter of 3 to 5 nm) is synthesized, multi-walled nanotubes, an iron layer with a thickness of 1 nm is deposited by evaporation with an electron gun. . This substrate just before the growth of the nanotubes can be optionally treated with a plasma. However, this treatment not a plasma is not mandatory and can be omitted. For example, this substrate can be treated by means of a succession of two air plasmas generally at a pressure of 0.3 mbar. This treatment aims to remove the parasitic carbon from the sample and oxidize the catalyst. The first plasma can be a plasma of 20 minutes duration with a power of 80 W, the second plasma can be a plasma of a duration of 20 minutes with a power of 30 W.
    [0049] The substrate is then introduced into a CVD chemical vapor deposition chamber. This deposition chamber may, in this embodiment where a carpet of small (ie with a diameter of 3 to 5 nm) nanotubes multi-wall, is synthesized comprise an array of 10 filaments mounted in parallel.
    [0050] The filaments are for example located 1 cm from the sample holder (sole) and spaced 1 cm apart. The gaseous mixture, composed for example of 20 sccm of acetylene, 50 sccm of hydrogen and 110 sccm of helium, is introduced cold at a pressure of, for example, 0.9 mbar. The hearth is brought to the temperature of 400 ° C. in 10 minutes and then a plateau is observed at this temperature. The filaments are heated by Joule effect with a power of 800W for example. Under these conditions after 20 minutes of bearing at the temperature of 400 ° C., a carpet of nanotubes having an average diameter of 4.5 nm and a height of 200 μm is obtained. If the bearing is increased to 45 minutes, carpets with a height of 400 μm are obtained. The density of the nanotubes on the substrate is generally greater than 1011 cm-2. According to a second embodiment, a carpet (1) of single-walled carbon nanotubes (2) can be synthesized on a surface (3) of a solid substrate (4).
    [0051] In this case with respect to the first embodiment of the synthesis of the nanotube mat: the thickness of the catalyst layer such as iron is reduced to 0.25 nm, the temperature of the heating floor is raised to 500 ° C. the number of filaments is reduced to 6, the gas mixture is composed of 5 sccm of acetylene, 200 sccm of hydrogen, and 200 sccm of helium. The other conditions of the synthesis of the nanotube mat are identical to those of the first embodiment of this synthesis.
    [0052] During this step of synthesizing the carbon nanotube mat NTCs, those skilled in the art can easily adapt the process conditions so as to obtain single-wall or multi-wall carbon nanotubes having the diameter, the grafting density of the NTCs, and the length of the desired NTCs, in wide ranges. Thus: ## EQU1 ## Pore Diameter: NTCs having a diameter in the range of 1 to 100 nm can be obtained. It is believed that the increase in diffusion coefficient and / or ionic conductivity is inversely proportional to the diameter of the NTCs. It is therefore preferred to obtain CNTs whose diameter is in the range 1 to 35 nm. Graft Density of NTCs: A graft density of 109 to 1013 cm-2 can be obtained. It will generally be sought to optimize the graft density of the NTCs so that it is as high as possible, for example in the range of 1011 cm-2 to 1013 cm-2. NTCs Length: NTCs with a length in the range of 10 microns to 100 mm, preferably 50 microns to 500 microns, for example 150 microns, can be obtained.
    [0053] After having synthesized the carpet (1) of carbon nanotubes (2) on a surface (3) of a solid substrate (4), this carpet is transformed into a membrane by filling / filling the space between the carbon nanotubes , NTCs, by a solid material such as an organic polymer also called matrix material (5) (Fig.
    [0054] 1B). In the case where the solid material is an organic polymer, or can dissolve this polymer in a suitable solvent to obtain a solution of the organic polymer in the solvent. The polymer such as polystyrene 350000 g / mol can for example be dissolved in toluene to obtain a solution at 20% by weight. The solution of the organic polymer is poured onto the CNT carpet, whereby it fills the gap between the carbon nanotubes, and then the solvent is allowed to evaporate. Alternatively, a solvent-free organic polymer can be used and heated, preferably under vacuum, above its glass transition temperature Tg, or its melting point, to thereby obtain a fluid or molten polymer. This fluid or molten polymer can be allowed to absorb in the intertube space by simple capillarity.
    [0055] If the solid material is a metal or a metal oxide then said metal or metal oxide can be deposited by one of the methods already mentioned above, such as an electrochemical deposition process or a sol-gel process, in which the space between the carbon nanotubes.
    [0056] Regardless of the solid material, the space between the carbon nanotubes can be filled by projecting said solid material into the space between the carbon nanotubes. According to another embodiment, instead of growing carbon nanotubes, all substantially parallel, and separated by a gap, on a surface of a substrate provided with a carbon nanotube growth catalyst, and then filling 10 completely said space between the carbon nanotubes by a solid material, one can in one step grow carbon nanotubes, all substantially parallel and separated, on a surface of a substrate and inside the pores of a material porous solid with oriented pores. Such porous solid material with oriented pores can be selected for example from porous aluminas, and growth can be achieved by a CVD chemical vapor deposition process. Subsequently, the substrate, any solid material in excess, is removed and the two ends (6, 7) of the carbon nanotubes (2) are opened (FIG.
    [0057] 1 C). The optional solid material in excess is essentially the excess solid material which covers the end (6) of the carbon nanotubes on the opposite side of the substrate. The elimination of the substrate, any solid material in excess, and the opening of both ends of the carbon nanotubes can be achieved by any suitable technique for example by mechanical polishing and / or plasma etching. Then, in a final step (not shown in FIG. 1), the interior of the nanotubes is filled with an electrolyte. The electrolyte has already been described above. As already indicated above, in the case where the electrolyte is a polymer that contains a conductive salt, it is called polymer electrolyte or polymer electrolyte.
    [0058] Any type of electrolyte polymer may be used, for example an alkaline salt solution in poly (oxyethylene). The mass of the poly (oxyethylene) may be in the range of 44 to 106 g / mol. Ionic salts and ionic liquids have already been listed above.
    [0059] The filling may be carried out simply by imbibing, spontaneously or under vacuum, the core, the inside of the NTCs in contact with the electrolyte, for example ionic liquid. In the case of a polymer electrolyte, it may be confined in the pores by immersing it in an excess of molten or liquid polymer electrolyte, preferably under vacuum and hot beyond the melting point of the electrolyte. .
    [0060] It can be said that the liquid polymer electrolyte penetrates the porous structure by simple capillarity. The electrolyte membrane, for example ionic liquid or polymer, according to the invention as described above can be used in any electrochemical system employing a polymer electrolyte (Figure 2).
    [0061] The electrolyte membrane comprises a first major surface (21) and a second major surface (22) separated by a thickness (23). Carbon nanotubes define pores or through-channels (24) open at both ends (25,26), with a diameter of less than or equal to 100 nm, oriented in the direction of the thickness (23) of the membrane and all substantially parallel, over the entire thickness (23) of the membrane. These pores or channels connect the first main surface (21) and the second main surface (22); and an electrolyte is confined in the pores (24) of the membrane. The electrochemical system may in particular be a rechargeable electrochemical accumulator such as an accumulator or a lithium battery, which in addition to the electrolyte membrane, as defined above, comprises a positive electrode; a negative electrode; generally current collectors (27,28), generally made of copper for the negative electrode, or of aluminum for the positive electrode, which allow the circulation of the electrons, and therefore the electronic conduction, in the external circuit (29); and generally a separator to prevent contact between the electrodes and thus the short circuits, these separators may be microporous polymer membranes. The negative electrode may be made of lithium metal as an electrochemically active material, in the case of lithium-metal accumulators, otherwise the negative electrode may comprise as electrochemically active material intercalation materials such as carbon graphite (Cgr), or lithium titanium oxide (Li4Ti5012) in the case of batteries based on lithium-ion technology. The positive electrode generally comprises, as electrochemically active material, lithium intercalation materials such as lithiated transition metal lamellar oxides, lithiated iron olivines or phosphates (LiFePO4) or spinels (e.g. spinel LiNi 0.5 Mni, 504). More specifically, the electrodes, in the case where they are not constituted by lithium metal, comprise a binder which is generally an organic polymer, an electrochemically active material of positive or negative electrode, optionally one or more additive (s) electronic conductor (s), and a current collector. In the positive electrode, the electrochemically active material may be chosen from the compounds already mentioned above in the present description; and among LiCoO2; compounds derived from LiCoO2 obtained by substitution preferably with Al, Ti, Mg, Ni and Mn, for example LiAlxNlyCo (1_x_y) O2 or x <0.5 and y <1, LiNixMnxCo1-2x02; LiMn204; LiNiO 2; Compounds derived from LiMn 2 O 4 obtained by substitution preferably with Al, Ni and Co; LiMnO2; compounds derived from LiMnO2 obtained by substitution preferably with Al, Ni, Co, Fe, Cr and Cu, for example LiNi0, 502; olivines LiFePO4, Li2FeSiO4, LiMnPO4, LiCoPO4; phosphates and iron sulphates, hydrated or not; LiFe 2 (PO 4) 3; hydrated or non-hydrated vanadyl phosphates and sulphates, for example VOSO4, nH2O and LixV0PO4, nH20 (0 <x <3, 25 0 <n <2); Li (1, x) V308, O <x <4, LixV205, nH2O, with 0 <x <3 and 0 <n <2; and their mixtures. In the negative electrode, the electrochemically active material may be chosen from the compounds already mentioned above in the present description; and among carbon compounds such as natural or synthetic graphites and disordered carbons; LiXM type lithium alloys with M = Sn, Sb, Si; LixCu6Sn5 compounds with 0 <x <13; iron borates; single oxides with reversible decomposition, for example CoO, Co203, Fe2O3; pnicures, for example Li (3_x_y) CoyN, Li (3_x_y) FeyN, LixMnP4, LixFeP2; LixFeSb2; and insertion oxides such as titanates, for example TiO 2, Li 4 Ti 5 O 12, LixNiP 2, LixNiP 3, MoO 3 and WO 3 and mixtures thereof, or any material known to those skilled in the art.
    [0062] The optional electronic conductive additive may be selected from metal particles such as Ag particles, graphite, carbon black, carbon fibers, carbon nanowires, carbon nanotubes and electronically conductive polymers. and their mixtures. The current collectors are generally copper for the negative electrode, or aluminum for the positive electrode. Figure 3 shows a particular embodiment of an accumulator such as a lithium battery according to the invention. This accumulator comprises a negative electrode (31), for example a lithium metal negative electrode, an electrolyte membrane according to the invention (32), and a positive electrode (33). The electrolyte membrane (32) comprises an electrolyte, for example an ionic liquid containing a lithium salt, confined in pores defined by carbon nanotubes, for example with a diameter of 2 to 8 nm. Since the electrolyte membrane according to the invention (32) comprises NTCs which are electronically conductive, the operation of the device possibly requires the insertion of a medium that is both porous and has good electrical insulation (34) between the membrane comprising NTCs ( 32) and one of the two electrodes. This porous insulating medium may for example be a porous membrane or a sol-gel type assembly. It is desirable, but not necessary, for the pores of this insulating porous medium to be macroscopically oriented. The pore diameter of this insulating porous medium must be greater than the diameters of the NTCs. As a porous membrane (34), a porous alumina membrane, such as an "Anodic Aluminum Oxide" or "AAO" membrane in the English language, can be used. These are ceramic membranes (very good electrical insulator) of a few centimeters, for example from 0.1 to 100 and a few hundred microns thick, for example from 1 to 500. In FIG. 3 such a porous alumina membrane (34) is interposed between the negative electrode (31) and the electrolyte membrane (32) according to the invention.
    [0063] FIG. 4 shows another particular embodiment of an accumulator such as a lithium battery according to the invention that can be called a "full 1D" lithium battery. This accumulator comprises a negative electrode (41) for example a lithium metal negative electrode, an electrolyte membrane according to the invention (42), and a positive electrode (43). The electrolyte membrane according to the invention (42) comprises an electrolyte, for example an ionic liquid containing a lithium salt, confined in pores defined by carbon nanotubes NTCs, for example with a diameter of 2 to 8 nm. But in this embodiment, during the preparation of the electrolyte membrane 15 and before the conversion of the NTCs mats into a membrane, the hybridization of the carbon atoms of the CNTs has been modified by grafting a polymer. As a result, the CNTs then become electronic insulators and the porous medium to be inserted between the electrolyte membrane according to the invention, and one of the electrodes becomes superfluous (see FIG.
    [0064] The positive electrode (43) of the accumulator according to this embodiment may be any known positive electrode, however in FIG. 4, the represented positive electrode (43) is an electrode obtained by functionalizing the CNT mats by means of electro-active species, redox species such as Anthraquinone AAQ. Accumulators which comprise the electrolyte membrane, for example polymer electrolyte, according to the invention can be used in particular for automotive propulsion such as batteries in electric or hybrid vehicles, such as batteries for the supply of portable electronic devices. such as computers, telephones, watches, and portable game consoles; more generally as batteries for the supply of electronic devices such as computers, video players, MP3 players, MP4 etc. ; as the batteries for the power supply 3034258 31 of electronic devices embedded for example on aircraft; like batteries for storing energy produced by intermittent electricity generating devices, such as wind turbines and solar panels. The invention will now be described with reference to the following examples, given by way of non-limiting illustration. EXAMPLES. Example 1
    [0065] In this example, an electrolyte membrane according to the invention is prepared. The process for preparing this electrolyte membrane according to the invention comprises four successive steps. Step 1.
    [0066] During this step (FIG. 1A), a carpet or forest of multi-walled carbon nanotubes is prepared or synthesized on a substrate by a chemical vapor deposition ("CVD" or "Chemical Vapor Deposition" method). . The growth substrate is a wafer of silicon on which is deposited by an ALD process ("Atomic Layer Deposition") a layer of alumina 20 nm thick. On this layer of alumina, a layer of iron with a thickness of 1 nm acting as a catalyst is deposited by evaporation with an electron gun. Just before proceeding with the growth of the nanotubes, the substrate provided with the iron layer undergoes two successive treatments by plasma air at a pressure of 0.3 mbar. The first treatment is a treatment lasting 20 minutes with a power of 80W, and the second is a treatment lasting 20 minutes at a power of 30W. The substrate is then introduced into a CVD vapor deposition chamber having an array of 10 filaments mounted in parallel.
    [0067] The filaments are located 1 cm from the sample holder, constituted by a sole, and they are spaced from each other by 1 cm. The filaments are heated by joule effect with a power of 800W. A gas mixture composed of 20 sccm of acetylene, 50 sccm of hydrogen and 110 sccm of helium is introduced cold into the CVD chamber at a pressure of 0.9 mbar. The sole is heated to a temperature of 400 ° C. in 10 minutes, then a plateau is observed at the temperature of 400 ° C. for a period of 20 minutes or 45 minutes. After having observed a plateau at 400 ° C. for a period of 20 minutes, a carpet of carbon nanotubes with an average diameter of 4.5 nm and a height of 200 μm is obtained. If the bearing is increased to 45 minutes, we obtain carbon nanotube mats also with an average diameter of 4.5 nm, but whose height, length is 400 μm. The density of the nanotubes on the surface of the substrate is greater than 1011 cm -1. FIG. 5 is a photograph taken with a scanning electron microscope of the carpet or forest of carbon nanotubes obtained at the end of step 1. Step 2. During this step, the carbon nanotube mat is converted into a membrane. by filling, filling the empty space between the carbon nanotubes NTCs of the carbon nanotube carpet, the forest of carbon nanotubes with a polymer (FIG.
    [0068] 1B). The polymer is polystyrene with a molecular weight of 350000 g / mol. This polymer is dissolved in toluene to obtain a 20% solution by mass. This solution is poured onto the carpet, the forest, with carbon nanotubes, and then the solvent is allowed to evaporate. At the end of this step, a membrane is obtained in which the carbon nanotubes are surrounded by a polymer matrix. Generally, the end of the carbon nanotubes opposite to the substrate is covered with polymer (FIG.
    [0069] 1B) and excess polymer is therefore present on the nanotubes.
    [0070] Step 3. During this step, a mechanical polishing of the two faces of the membrane obtained in step 2 is carried out in order to eliminate the excess polymer, to eliminate the substrate and to open the nanotubes of the carbon at both ends (FIG.
    [0071] 1 C). Figure 6 is a scanning electron micrograph of the membrane obtained at the end of step 3. Step 4.
    [0072] During this step, the interior, the core, is filled with carbon nanotubes by an ionic liquid, namely 1-octyl-3-methylimidazolium tetrafluoroborate (OMIMBF4). The filling is carried out by simple spontaneous imbibition or vacuum of the core of the NTCs in contact with the ionic liquid.
    [0073] In Examples 2 and 3 which follow, the properties of the membrane according to the invention prepared in Example 1 were measured. In Example 2, the diffusion coefficient or, more exactly, the coefficient of self-diffusion ( "Self-diffusion coefficient") of the ionic liquid confined in the carbon nanotube membrane prepared in Example 1 was measured at room temperature.
    [0074] The measurement was made by pulsed field gradient magnetic resonance (NMR) of Fluorine 19 (Fig. 7). In Example 3, the conductivity of the ionic liquid confined in the carbon nanotube membrane was measured at room temperature. The measurement was made by impedance spectroscopy (Figs 8 and 9).
    [0075] EXAMPLE 2 In this example, the diffusion coefficient of the ionic liquid confined in the membrane of carbon nanotubes NTCs prepared in Example 1 was measured at room temperature.
    [0076] The measurement is made by pulsed field gradient magnetic resonance (NMR) of Fluorine 19 (Fig. 7). For comparison purposes, the diffusion coefficient of the same ionic liquid as that contained in the pores of the NTC membrane of Example 1, namely 1-octyl-3, is also measured at room temperature. methylimidazolium tetrafluoroborate, (OMIMBF4), but not confined in the pores. This non-confined ionic liquid is also called ionic liquid "volume" or "bulk" ("bulk"). The results of these measurements are shown in FIG. 7. This figure shows that, at room temperature, the self-diffusion coefficient of the ionic liquid (1-octyl-3-methylimidazolium tetrafluoroborate, OMIMBF4) confined according to the invention in a membrane of carbon nanotubes whose average internal pore diameter is 4 nm, is about 3 times greater than the self-diffusion coefficient of the same non-confined ionic liquid, volume. In other words, an approximately three-fold increase in the self-diffusion coefficient due to confinement is obtained because this self-diffusion coefficient is 4.4 (+/- 0.3) 10-8 cm 2s -1 for the ionic liquid volume, and 1.3 (+/- 0.2) 10-7 cm2s-1 for the same ionic liquid confined in the membrane. Example 3
    [0077] In this example, the conductivity of the ionic liquid confined in the membrane of carbon nanotubes NTCs prepared in Example 1 is measured at room temperature. The measurement is made by impedance spectroscopy (Fig. 8). For comparison purposes, the conductivity of the same ionic liquid as that contained in the pores of the NTC membrane of Example 1, namely 1-octyl-3-methylimidazolium tetrafluoroborate, is also measured at room temperature. , (OMIMBF4), but not confined in the pores. This non-confined ionic liquid is also called ionic liquid "volume" or "bulk" ("bulk"). The block diagram of the device which made it possible to measure by impedance spectroscopy, at room temperature, the conductivity of the unconfined bulk volume OMIMBF4 ionic liquid and in a membrane of carbon nanotubes is shown in FIG. 8. This device comprises an upper electrode (71), and a lower electrode (72) separated by a distance L. Between these two electrodes (71, 72) is placed the membrane according to the invention, prepared in Example 1 (73). ), which comprises carbon nanotubes (74) (for convenience a single carbon nanotube has been shown) within which the ionic liquid OMIMBF4 (75) is confined in a polystyrene matrix (76). To ensure perfect electrical contact between the membrane (73) confining the ionic liquid (75) (the confined ionic liquid is also denoted "IL @ NTC" and its impedance is Zit @ N-rc) and the electrodes (71, 72 ), an excess of ionic liquid volume also called bulk liquid (noted "bulk") of a known thickness, namely of the order a few millimeters is maintained on each side of the membrane. Thus, between the lower surface of the electrode (71) and the membrane is volume ionic liquid (77) of known thickness E1 (79), and between the membrane (73) and the lower surface of the electrode (72) is of volume ionic liquid (78) of the same known thickness E2 equal to El (710). The total impedance of the ionic liquid by volume of a total thickness E1 + E2 is Zbuk. The active surface (711) of the ionic liquid (77) or (78) can be designated by S.
    [0078] The impedance of the volume ionic liquid (77) of a known thickness E1 (79), and the impedance of the volume ionic liquid of known thickness E2 (710) is therefore Zbuk / 2. The total impedance Ztot of the system consisting of the ionic liquid in volume, and the confined ionic liquid is therefore the following: Ztot = Zboik + Zit @ NTc.
    [0079] The results of the measurements carried out in this example are shown in FIG. 9, which gives the Cole-Cole Representation of the bulk electrolyte electrical impedance and the confined electrolyte in the nanotubes. a membrane comprising carbon nanotubes in a polystyrene matrix. To give an estimate of the uncertainty of the measurement, in each case two successive measurements are represented.
    [0080] 3034258 36 The electrical impedance of the electrolyte in volume (Zbulk) and the total impedance of the system (Zte). are shown in Figure 9. The resistance of the ionic liquid confined in the membrane NTC nanotubes is ZIL @ NTC-PS = Ztot - Zbulk 1500-1000 = 500 Q.
    [0081] RNTc = 1.5 nm, pwc = 3.0 X 10 11 NTC / cm 2, eNTc = 125 lm, and S = 0.5 cm 2, respectively are the inner radius, the surface density, the length of the CNTs (or equivalently the thickness of the membrane), and the effective contact area between the electrodes and the membrane comprising carbon nanotubes in a polystyrene matrix.
    [0082] The conductivity of the confined electrolyte in the membrane comprising carbon nanotubes in a polystyrene matrix is alL @ Nrc_ps = n-c / (ZiL @ Nrc-ps x Tt RNTC2 x plot) / S = 0.236 S / m. The conductivity of the bulk electrolyte under the same conditions is IL bulk = 0.07 S / m.
    [0083] Under confinement, the conductivity gain is therefore 3.4 ± 1. Examples 3 and 4 show that the confinement of the electrolyte makes it possible to obtain a self-diffusion coefficient ("self-diffusion coefficient") and consequently an ionic conductivity of the upper electrolyte (here a factor of 3 is shown). 4) to those of the bulk electrolyte. 20
    权利要求:
    Claims (27)
    [0001]
    REVENDICATIONS1. A porous membrane comprising a first main surface (1) and a second main surface (2) separated by a thickness (3) in which: - carbon nanotubes (4), defining pores or open channels at both their ends (5) , 6), of a diameter less than or equal to 100 nm, oriented in the direction of the thickness (3) of the membrane and all substantially parallel, over the entire thickness (3) of the membrane, connect the first major surface (1) and the second major surface (2); the carbon nanotubes are separated by a space, and said space between the carbon nanotubes is completely filled with at least one solid material.
    [0002]
    The membrane of claim 1, wherein an electrolyte is confined within the carbon nanotubes.
    [0003]
    A membrane according to any one of the preceding claims, wherein the first and second major surfaces are planar and parallel, the membrane is a planar membrane, and the nanotubes, pores or channels are substantially aligned, or aligned, perpendicularly. to said surface.
    [0004]
    4. Membrane according to any one of the preceding claims, in which the carbon nanotubes are functionalized on their outer wall in order to render them insulating electronically, for example by fluorination, or by means of an organic compound which renders them insulating electrons, as an aryl diazonium; or the carbon nanotubes are functionalized on their outer wall by redox species, such as anthraquinones, and / or electroactive species such as ferrocenepyrene. 3034258 38
    [0005]
    5. Membrane according to any one of the preceding claims, wherein the nanotubes have an inner diameter of 1 to 100 nm, preferably 1 to 20 nm, more preferably 1 to 3 nm. 5
    [0006]
    6. Membrane according to any one of the preceding claims, wherein the carbon nanotubes and the pores or channels have a length of 10 microns to 100 mm, preferably 50 microns to 500 microns, for example 150 microns.
    [0007]
    A membrane according to any one of the preceding claims, wherein the solid material is selected from electronic insulating materials or from electronic conductive materials whose outer surface, in contact with the outside of the membrane, has been electronically rendered insulating.
    [0008]
    8. Membrane according to any one of claims 1 to 7, wherein the solid material is selected from organic polymers, metals and metal oxides.
    [0009]
    A membrane according to any one of the preceding claims, wherein the electrolyte is selected from a proton carrier or proton conductor such as a protonic ionic liquid or a proton conductive polymer, a zwitterionic ionic liquid, an acid dissolved in an organic polymer, an ionic liquid, an ionic liquid containing an ionic conductive salt such as an alkali metal salt or a salt of an alkaline earth metal, a liquid organic solvent or an organic polymer containing an ionic conductive salt such as an alkali or alkaline earth metal salt, an ionic liquid in an organic polymer, a mixture of an organic polymer and an organic solvent, a mixture of an ionic liquid and an organic solvent, a mixture an ionic liquid, an organic solvent and a salt of an alkali or alkaline earth metal, a mixture of an organic polymer, an organic solvent and an alkali metal salt or alkaline earth metal, a mixture of a salt of an alkali metal or alkaline earth metal, for example lithium in a protic ionic liquid; or a combination of several of the above electrolytes.
    [0010]
    10. The membrane of claim 9, wherein the organic polymer is a polymer which allows good solvation of alkali metal ions such as Li or alkaline earth metal ions, for example the organic polymer is selected from homopolymers and copolymers of ethylene oxide, and their derivatives.
    [0011]
    The membrane of claim 9 or 10, wherein the organic polymer has a molecular weight of less than 106 g / mol, preferably less than 105 g / mol, more preferably less than its critical entanglement mass.
    [0012]
    The membrane of claim 9, wherein the ionic conductive salt is an alkali metal salt, for example a lithium salt or a sodium salt; or a salt of an alkaline earth metal, for example a magnesium salt.
    [0013]
    The membrane of claim 12, wherein the ionic conductive salt is a lithium salt selected from LiAsF6, LiClO4, LiBF4, LiPF6, LiBOB, LiODBF, LiB (C6H5), LiRFSO3, for example LiCF3SO3, LiCH3SO3, LiN (RFSO2). 2 for example LiN (CF3SO2) 2 (LiTFSI) or LiN (C2F5SO2) 2 (LiBETI), LiC (RFSO2) 3, for example LiC (CF3SO2) 3 (LiTFSM), in which RF is selected from a fluorine atom and a perfluoroalkyl group comprising from 1 to 9 carbon atoms, LiTFSI is the acronym for lithium bis (trifluoromethylsulfonyl) imide, LiBOB that of lithium bis (oxalato) borate, and LiBETI that of lithium bis (perfluoroethylsulfonyl) imide, or a salt of analog sodium to lithium salts previously listed but comprising a sodium ion instead of a lithium ion.
    [0014]
    14. Membrane according to any one of claims 9, 12 and 13, wherein the concentration of ionic conductive salt in the electrolyte is 1 to 50% by weight relative to the mass of the electrolyte. 3034258 40
    [0015]
    15. Membrane according to any one of claims 2 to 14, wherein the electrolyte completely fills the carbon nanotubes.
    [0016]
    16. A method for preparing the electrolyte membrane according to any one of claims 1 to 15, wherein the following successive steps a) and b) are carried out: a) growing carbon nanotubes, all substantially parallel, and separated by a gap, on a surface of a substrate provided with a carbon nanotube growth catalyst; b) said space between the carbon nanotubes is completely filled with a solid material; or else the following step a1) is carried out: a1) carbon nanotubes, all substantially parallel and separated, are grown on a surface of a substrate and inside the pores of a porous solid material with pores oriented; Then, at the end of step b) or of step a1), the following step c) is carried out c) the substrate is eliminated, any excess solid material in excess, and the two ends of the carbon nanotubes.
    [0017]
    17. The method of claim 16, wherein, after step c), the interior of the nanotubes is filled with an electrolyte.
    [0018]
    18. The method of claim 16 or 17, wherein the growth substrate is a silicon wafer, or a strip of stainless steel or aluminum on which is deposited a layer of alumina, and the catalyst of Growth of the carbon nanotubes is deposited on the alumina layer.
    [0019]
    19. Process according to any one of claims 16 to 18, in which the growth catalyst of carbon nanotubes is chosen from iron, nickel, cobalt, and their alloys. 3034258 41
    [0020]
    20. Process according to any one of claims 16 to 19, wherein the carbon nanotubes are grown by a CVD chemical vapor deposition process.
    [0021]
    21. A process according to any one of claims 16 to 20, wherein the solid material is an organic polymer and step b) is carried out either by dissolving the organic polymer in a solvent to form a solution of the organic polymer, completely filling the space between the carbon nanotubes with the solution of the organic polymer and evaporating the solvent; either by heating the organic polymer in the absence of solvent above its glass transition temperature (Tg) or its melting point to make it fluid, and allowing the fluid polymer to absorb in the space between carbon nanotubes; either filling the gap between the carbon nanotubes with a mixture comprising organic monomers (such as styrene, methyl methacrylate, or the like), or organic oligomers modified with reactive functions, or organic copolymers, and in addition, one or more photosensitive and / or thermally sensitive free radical initiator (s); and then crosslinking said mixture thermally or by means of photon radiation. 20
    [0022]
    22. A method according to any one of claims 16 to 21, wherein the solid material is a metal, and then step b) is performed by depositing said metal by an electrochemical deposition process in the space between the nanotubes of or the solid material is a metal oxide and then step b) is carried out by depositing said metal oxide by an electrochemical deposition process, or by a sol-gel process, in the space between the carbon nanotubes.
    [0023]
    23. A method according to any one of claims 16 to 21, wherein step b) is carried out by projecting said solid material into the space between the carbon nanotubes. 3034258 42
    [0024]
    24. A method according to any one of claims 16 to 23, wherein step c) is performed by mechanical polishing and / or plasma etching.
    [0025]
    25. An electrochemical device comprising an electrolyte membrane according to any one of claims 2 to 15.
    [0026]
    26. A lithium battery, such as a lithium metal battery or a lithium-ion battery, comprising an electrolyte membrane according to any one of claims 2 to 15, a positive electrode, and a negative electrode.
    [0027]
    27. Use of the membrane according to claim 1, for filtering a fluid, in particular for filtering a liquid. 10
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    公开号 | 公开日
    US10615453B2|2020-04-07|
    US20180115014A1|2018-04-26|
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    EP3275037A1|2018-01-31|
    FR3034258B1|2021-12-17|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1552572A|FR3034258B1|2015-03-26|2015-03-26|POROUS MEMBRANE, IN PARTICULAR ELECTROLYTE MEMBRANE OR FILTRATION MEMBRANE, ITS PREPARATION PROCESS, AND ELECTROCHEMICAL DEVICES INCLUDING IT.|FR1552572A| FR3034258B1|2015-03-26|2015-03-26|POROUS MEMBRANE, IN PARTICULAR ELECTROLYTE MEMBRANE OR FILTRATION MEMBRANE, ITS PREPARATION PROCESS, AND ELECTROCHEMICAL DEVICES INCLUDING IT.|
    US15/560,516| US10615453B2|2015-03-26|2016-03-25|Porous electrolyte membrane, manufacturing process thereof and electrochemical devices comprising same|
    PCT/EP2016/056732| WO2016151142A1|2015-03-26|2016-03-25|Porous electrolyte membrane, manufacturing process thereof and electrochemical devices comprising same|
    EP16715266.9A| EP3275037A1|2015-03-26|2016-03-25|Porous electrolyte membrane, manufacturing process thereof and electrochemical devices comprising same|
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