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    • 专利摘要:
    Electrode for a lithium accumulator, or lithium battery, comprising: - an active electrode material, based on silicon, - a conductive agent, - a binder comprising a mixture of two polymers: ○ the first polymer having a first molecular weight , the first polymer being a first polyacrylate or one of its derivatives, ○ the second polymer having a second molecular weight, the second polymer being a second polyacrylate or a carboxymethyl cellulose, or one of their respective derivatives.
    公开号:FR3048821A1
    申请号:FR1651917
    申请日:2016-03-08
    公开日:2017-09-15
    发明作者:Willy Porcher；Frederic Barbier；Sophie Chazelle；Nicolas Mariage；Leo Merchat
    申请人:Umicore NV SA；Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    Lithium-ion battery electrode comprising a binder formed from a mixture of two polymers, the first polymer being a first polyacrylate or a derivative thereof, the second polymer being a second polyacrylate or a carboxymethyl cellulose or a derivative thereof, ink for the realization of such an electrode.
    TECHNICAL FIELD OF THE INVENTION The invention relates to a lithium-ion battery electrode comprising a binder formed from a mixture of two polymers: the first polymer is a first polyacrylate or one of its derivatives, the second polymer is a second polyacrylate or a carboxymethyl cellulose or a derivative thereof. The invention also relates to an ink for producing such an electrode. State of the art
    As represented in FIG. 1, the lithium accumulators are conventionally constituted by an electrochemical cell 1 disposed in a housing 2. The electrochemical cell 1 is formed by a negative electrode 3 and a positive electrode 4, separated by an electrolyte 5. Each of the positive and negative electrodes, respectively 3 and 4, is in contact with a current collector, 6a or 6b, which transports the electrons to an external electrical circuit (not shown). Depending on the type of lithium battery, the electrolyte 5 may be in solid, liquid or gel form.
    A battery is formed of several accumulators.
    The electrodes 3 and 4 are generally made by coating an ink, comprising the electrochemically active powder material, a binder and an electronic conductor, dispersed in an organic or aqueous solvent, on the current collector 6a or 6b. The coating step is conventionally followed by drying the ink / current collector assembly to remove traces of solvent contained in the ink. The electrode thus obtained adheres to the current collector.
    The electronic conductor is used to improve the electronic conductivity of the electrodes 3 and 4.
    The binder makes it possible to confer on the electrode the cohesion of the various components of the electrodes and its mechanical resistance on the current collector. It also confers a certain flexibility on the electrode for its implementation in cells, particularly with respect to the winding step, for the wound elements.
    The electrochemically active negative electrode material is formed of a metal or semi-metal capable of forming an alloy with lithium. It is, in particular, silicon.
    These types of material have a very high theoretical specific capacity (of the order of 3580 mAh / g for silicon) compared with that of graphite (of the order of 370 mAh / g).
    However, these materials exhibit a high volume expansion during lithiation. This expansion will cause the degradation of the Li-ion cell based on this material to the negative electrode: i) degradation of the integrity of the electrode which leads to a decrease in the capacity of the electrode, ii) fracture of the electrode-electrolyte interface (or SEI for "solid electrolyte interface") which leads to the continuous formation of degradation product, iii) addition of constraints on the entire battery and degradation of the other components .
    To prevent degradation of the electrode and to improve the electrochemical performance of the battery, many studies have focused on the nature of the binder.
    The polymeric binders for electrodes commonly used at present are soluble polymeric binders: either in organic solvents such as polyvinylidene fluoride, denoted PVDF, or in an aqueous solvent such as carboxymethyl cellulose, denoted CMC, nitrile rubber. (In English "nitrile butadiene rubber", noted NBR), styrene-butadiene rubber (in English "styrene butadiene rubber", denoted SBR), or polyacrylic acid (PAA) or polyacrylate according to its degree of dissociation.
    The polymeric binders soluble in an aqueous solvent are preferred because they avoid the use of combustible, volatile, flammable and toxic organic solvents, sometimes classified as Carcinogenic Reprotoxic Mutagenic (CMR) and whose use requires the establishment of special handling conditions. .
    A polymeric binder is characterized by its chain length, conventionally by the molecular weight in g / mol, Mw:
    With: ηχ, the number of macromolecules with degree of polymerization x,
    Mx the mass of such macromolecules.
    The molecular weight, or molecular weight, of polymer is defined as a mean mass. The molecular masses are generally distributed according to a Gaussian curve centered on the molecular mass defining it.
    In order to maintain the integrity of the electrode, a binder with a relatively high Young's modulus and sufficient elasticity, such as PAA or CMC, is preferred.
    CMC and PAA are both polymers with a carbon chain. The carbon chain has carboxylic groups, on each monomer, for PAA. For the rigid carbon chain of the CMC, there is a partial substitution of certain OH groups.
    The performances, in terms of coulombic efficiency, in particular, are better with the PAA (thesis of Etienne Radvanyi, defended in 2014, University of Grenoble, «Understanding of the mechanisms of (de) lithiation and degradation of silicon electrodes for accumulator Li-ion and study of influential factors "). The PAA binder would advantageously combine good physicochemical interactions with the active ingredient and a high Young's modulus, as well as sufficient elasticity, thus making it possible to optimally preserve the integrity of the electrode.
    It is known to integrate the PAA as a binder in silicon-based negative electrode formulations in order to overcome the problem of expansion and contraction of the electrochemically active material. Polyacrylic acid or polyacrylate, according to its degree of dissociation, used in these formulations, has different molecular weights: 250000 g / mol (thesis cited above), 750000 g / mol (J. Phys Chem C 2011, 115, 13487 -13495), 1250000 g / mol (Energy Environ Sci., 2012, 5, 9014-9020), between 300000 g / mol and 3000000 g / mol (US 2007/0026313), between 1000000 g / mol and 1250000 g / mol (US 2013/0236778), 2000 g / mol, 5000 g / mol or 100,000 g / mol (Appl Interfaces Mater, 2010, 2, 11,3004-3010).
    However, even if the use of the PAA makes it possible at the same time to reduce the formation of the electrode-electrolyte interface and to stabilize it, it appears that the production of electrodes by means of the aforementioned inks is difficult to implement. . The electrode inks made from these grades of PAA do not, in certain cases, make it possible to incorporate significant proportions of PAA, typically more than 2% by weight, or in other cases, to confer on the electrode ink of the rheological properties adapted to the coating technique conventionally used for producing the electrodes.
    OBJECT OF THE INVENTION The object of the invention is to overcome the drawbacks of the prior art and, in particular, to propose a mechanically stable electrode, sufficiently flexible to be assembled, and having improved electrochemical properties as well as an ink. easy to deposit, and to obtain, after drying, such an electrode.
    This object is achieved by an electrode for a lithium battery, or for a lithium battery, comprising: - an electrode active material, based on silicon, - a conductive agent, - a binder comprising a mixture of two polymers: O the first polymer having a first molecular weight, the first polymer being a first polyacrylate or a derivative thereof, O the second polymer having a second molecular weight, the second polymer being a second polyacrylate or a carboxymethyl cellulose, or a respective derivative thereof.
    This object is also achieved by an ink for the production of a lithium-ion battery electrode comprising: an electrode active material, based on silicon, a solvent, a conductive agent, a binder comprising a mixture of two polymers: ο the first polymer having a first molecular weight, the first polymer being a first polyacrylate or one of its derivatives, O the second polymer having a second molecular weight, the second polymer being a second polyacrylate or a carboxymethyl cellulose, or one of their respective derivatives.
    Advantageously, the first polymer and the second polymer are polyacrylates or a derivative thereof.
    Advantageously, the first polymer and the second polymer are polyacrylates.
    Advantageously, the first polymer is a polyacrylate and the second polymer is a carboxymethyl cellulose.
    Advantageously, the first molecular weight is less than or equal to 400,000 g / mol and greater than or equal to 150,000 g / mol.
    Advantageously, the second molecular weight is advantageously greater than or equal to 650,000 g / mol and less than or equal to 4,000,000 g / mol, and still more advantageously, the second molecular weight is greater than or equal to 650,000 g / mol and less than or equal to at 1,500,000g / mol.
    Advantageously, the degree of dissociation of the polymers ranges from 35% to 100%.
    Advantageously, the first polymer and the second polymer are polyacrylates, the first molecular weight being greater than or equal to 250,000 g / mol and less than or equal to 400,000 g / mol, the second molecular weight being greater than or equal to 1,000,000 g / mol and less than or equal to 1,500,000g / mol, and the degree of dissociation of the polymers being greater than 90%.
    Advantageously, the first molecular weight is at most 67% by mass relative to the second molecular weight.
    Advantageously, the binder consists of the two polymers.
    Advantageously, the binder represents from 2% to 15% relative to the total weight of the electrode.
    Advantageously, the binder represents from 4% to 10% relative to the total weight of the electrode.
    Advantageously, the silicon is in the form of nanoparticles, the silicon being optionally inserted in a micrometric matrix, and being capable of forming an alloy with lithium LixSi type, with x between 0 and 3.75.
    Advantageously, 90% of the silicon in the form of nanoparticles has a size distribution of less than 300 nm.
    Advantageously, 50% of the silicon in the form of nanoparticles has a size distribution of less than 150 nm.
    Advantageously, the electrode has a basis weight ranging from 2.5 mg / cm 2 to 10 mg / cm 2 of deposited active material and a density of at least 1.4.
    Advantageously, the electrode is devoid of latex.
    BRIEF DESCRIPTION OF THE DRAWINGS Other advantages and features will become more clearly apparent from the following description of particular embodiments of the invention given by way of nonlimiting example and represented in the accompanying drawings, in which: FIG. , schematically and in section, a lithium accumulator according to the prior art, - Figures 2, 3a, 4a are graphs showing the viscosity (η) of different inks and solutions as a function of the shear gradient (γ), FIGS. 3b and 4b are graphs representing the viscous modulus (G ") and the elastic modulus (G ') of different inks as a function of the frequency (f); FIG. 5 represents coulombic efficiency (CE) in a function of the number of cycles for an electrode comprising a binder of a first polyacrylate of molecular weight 250,000g / mol and a second polyacrylate of a molecular weight of 1,250,000g / mol with a degree of dissociation of 100% (electrode G) in button cell.
    Description of a preferred embodiment of the invention The ink for producing a lithium-ion battery electrode comprises: an electrode active material, a solvent, advantageously water, an agent, electronic conductor, a binder comprising a mixture of two polymers: the first polymer having a first molecular weight, the first polymer being a first polyacrylate or a derivative thereof, the second polymer having a second molecular weight, the second polymer being a second polyacrylate or carboxymethyl cellulose, or a respective derivative thereof. - optionally, in addition, an additive.
    According to a preferred embodiment, the ink consists of: - the electrode active material, based on silicon, - the solvent, - the electronically conductive agent, - the binder comprising the mixture of the two polymers.
    The electrode active material is a negative electrode material used in lithium batteries. The negative electrode material comprises at least one metal or semi-metal M capable of forming an alloy with lithium LixM type with x between 0 and 5. The metal or semi-metal is advantageously silicon, aluminum, tin or germanium. Preferably, the electrode active material is based on silicon.
    To preserve the integrity of the material during the cycling, the silicon is advantageously in the form of nanoparticles.
    Silicon is in nanometric form, preferably in the form of nanoparticles to limit spray phenomena. Advantageously, 90% of its size distribution is less than SOOnm, and preferably 50% of its size distribution is less than 150 nm. The size distribution is a volume distribution.
    To preserve its integrity, silicon can also be integrated as nanoparticles in a micrometric matrix. By micrometric matrix is meant a matrix of micrometric size, that is to say a matrix having a size ranging from 0.1 μm to 50 μm, and advantageously a size ranging from 2 μm to 10 μm. .
    The micrometric matrix may be a carbon matrix or a metal matrix (Fe, Al, Co, Ni, Mn, Sn, Ge, etc.).
    The matrix may be predominant in weight relative to silicon. Advantageously, this matrix represents at least 50% of the mass. Most advantageously, this matrix represents at least 80% of the mass. The integration of nanoscale silicon particles in a micrometric matrix leads to the formation of a composite material, making it possible to reduce the impact of repeated optical expansions.
    Silicon is capable of forming an alloy with LixSi-type iithium, with X ranging from 0 to 3.75.
    The active material may also be a mixture of a silicon-based compound and another compound, such as graphite for example.
    The weight percentage of electrochemically active material is greater than or equal to 85% and, preferably, greater than or equal to 90% by weight of the dry electrode. The ink may, in some embodiments, include an additive, also referred to as an additional component.
    It may be an additional polymer, such as carboxymethyl cellulose, latex to improve the flexibility of the electrode, or a crosslinking agent such as polyvinyl alcohol (or PVA for "PolyVinyl Alcohol"). According to another alternative, this other component may be a polyacrylate (PAA) of another molecular weight. The ink then comprises three PAAs of different molecular weights.
    This other component represents 5% or less of the electrode, and preferably 3% or less.
    The different mass percentages expressed, unless otherwise indicated, are based on the sum total of the weights of the following compounds: the electrode active material, the electronically conductive agent, the binder and, optionally, the additive.
    The sister is not taken into account. Since the solvent evaporates during the process for producing the electrode, the mass percentages relative to the ink and to the electrode are thus identical. The weight of the compounds of the ink is here defined with respect to the electrode.
    More precisely, the weight of the electrode or the weight of the dry electrode means the weight of the various compounds once the ink has been coated and the solvent has evaporated. We also speak of dry extract. The conductive agent is, advantageously, carbon in divided form, in the form of spherical particles, or in the form of fibers, for example. The conductive agent may contain one or more electronic conductive materials. The electronic conductor is preferably selected from carbon black, carbon fibers, ultra-divided carbon and a mixture thereof. By ultra-divided carbon is meant carbon having a very large surface area.
    The binder represents from 2% to 15% of the weight of the dry extract, or the weight of the dry electrode, and preferably from 4% to 10% by weight of the dry extract. The ink is remarkable in that the binder comprises a mixture of two polymers: the first polymer having a first molecular weight, the first polymer being a first polyacrylate or a derivative thereof, the second polymer having a second molecular weight, the second polymer being a second polyacrylate or carboxymethyl cellulose, or a respective derivative thereof.
    The molecular weights of the first and second polymers are different. The second molecular weight is greater than the first molecular weight. Advantageously, the first molecular weight is at most 67% by mass relative to the second molecular weight, or even at most 50% relative to the second molecular weight.
    By derivative of polacrylate is meant a polymer or co-polymer based on at least 50% of the acrylate function:
    with R corresponding to a cation such as lithium, sodium, ammonium, or potassium in its dissociated form (polyacrylate). R is H in its undissociated form (polyacrylic acid).
    The carboxylic groups of the PAA are dissociated from an undissociated form by adding LiOH, NaOH, NH4OH or KOH.
    The degree of dissociation is the ratio between the number of carboxylate groups and the number of carboxylic and carboxylate groups.
    The degree of dissociation of the polymers is advantageously from 35% to 100%. To reach this degree of dissociation of LiOH, NaOH, NH4OH or KOH is added in a solution of PAA in such a way as to neutralize, according to the target degree, between 35 and 100% of the carboxylic groups.
    The pH of the solvent can be modified to control the degree of dissociation of the binder. The pH can be an indicator for estimating the degree of dissociation of the binder.
    The macromolecules of PAA then adopt a conformation in solution more unwound with respect to lower degrees of dissociation. The ink is then more viscous and it also has a more pronounced rhéo-fuidifiant behavior. This is then beneficial to electrochemical performance.
    By derivative of the CMC is meant a polymer or co-polymer based on at least 50% of the following monomer:
    With R being a mixture of H, CH2COOH, CH2COOU, CH2COONa, or OR, ONa, or OH. Alginate is, for example, a derivative of CMC.
    The degree of dissociation of the polymers ranges from 35% to 100%.
    The binder is advantageously composed of the two polymers.
    According to one embodiment, the first polymer is a polyacrylate and the second polymer is a carboxymethyl cellulose.
    The molecular weight of the polyacrylate is advantageously greater than or equal to 150,000 g / mol and less than or equal to 400,000 g / mol.
    The molecular weight of the CMC is advantageously between 650,000 g / mol and 4,000,000 g / mol, and even more advantageously between 650,000 g / mol and 1,500,000 g / mol.
    According to another embodiment, the first polymer and the second polymer are polyacrylates or a derivative thereof.
    Even more preferably, the first polymer is a PAAi polyacrylate and the second polymer is a PAA2 polyacrylate.
    These inks have improved rheological properties compared to inks containing only one polyacrylate, so they are easier to deposit by coating. At the same time, they allow a greater incorporation of PAA into the ink, leading to electrodes having better electrochemical properties.
    Preferably, the first molecular weight of PAAi is less than or equal to 400,000 g / mol. It is, preferably, greater than or equal to 150,000g / mol.
    These PAAs can be added in large quantities in the ink because their addition does not significantly increase the viscosity.
    Preferably, the second molecular weight of PAA2 is greater than or equal to 650,000 g / mol. It is preferentially less than or equal to 4,000,000g / mol. Even more preferentially, the second molecular weight of PAA 2 is greater than or equal to 650,000 g / mol and less than or equal to 1,500,000 g / mol.
    For higher molecular weights, it is necessary to incorporate more water into the ink to have a suitable viscosity. The drying stresses are then greater, which decreases the quality of the electrode. Advantageously, the average molecular weight PAA greater than 650,000 g / mol are constituted by sufficiently long polymer chains to give a rheo-fluidifying character to the ink.
    Preferentially, the first polymer and the second polymer are polyacrylates, the first molecular weight being greater than or equal to 250,000 g / mol and less than or equal to 400,000 g / mol, the second molecular weight being greater than or equal to 1,000,000 g / mol and less than or equal to 1,500,000g / mol, and the degree of dissociation of the polymers being greater than 90%.
    The weight ratio PAA1 / PAA2 is greater than or equal to 1, that is to say that the PAA mixture is made with at most 50% of the highest molecular weight PAA. The lowest molecular weight PAA is predominant, which leads to an ink that is easier to deposit because it is less viscous than in the case where the PAA of the highest molecular weight is the majority.
    If the PAAi is used alone, the ink is too viscous and if the PAA2 is used alone, the ink is not sufficiently rheo-thinning. A mixture of PAA is necessary to reach such ranges and to be able to make an electrode.
    The inks, prepared with such PAA mixtures, have a viscosity of 0.5 Pa.s at 5 Pa.s for a shear of 100%. They have a yield point of a few Pa.s.
    The viscosity of these inks for 0.1 sec shear is greater than 10 times the ink viscosity for 100s shear, i.e., the ink will have a viscosity greater than 5 Pa. s at 0.1 s
    Such inks exhibit a rheo-thinning behavior, with an infinite viscosity at rest, that is to say with a viscosity such that the movement of the particles of active material is blocked at rest. These inks are particularly suitable for producing an electrode by coating.
    For an ink having only a PAA of molecular weight greater than 650,000g / mol, and a degree of dissociation between 35 and 100%, the ink will have good rheological properties.
    However, the PAA can not be integrated in significant proportions to limit the constraints during drying and thus ensure good mechanical properties to an electrode having a basis weight of at least 2.5 mg / cm 2 of active material, it is i.e., at least 2.5 mg / cm 2 of electrode active material. In addition, it will be difficult to guarantee a dry extract high in ink.
    The performance of this electrode will be poor. Conversely, in the case of an ink comprising only PAA with a molecular weight of less than 400,000 g / mol, and a degree of dissociation of between 35 and 100%, the PAA can be integrated in significant proportions. the order of 2 to 15%, but the PAA will not confer good rheological properties to the ink, making its coating poor and inhomogeneous.
    The rheo-thinning character of PAA can be judged from solution containing only PAA. Solutions having different concentrations of PAA and having a degree of dissociation of 100% were developed and their viscosities measured under the conditions described above.
    The PAA alone must have a viscosity of between 0.5 and 2 Pa.s at 100% in order to obtain a viscosity of the final ink of between 0.5 and 5 Pa.s. It must also exhibit a rheo-fluidizing behavior with a viscosity at 0.15% ten times greater than that at 100%. The same properties are desired for the ink. The curves obtained are shown in FIG.
    Different solutions have been studied (Figure 2). Their rheological properties are listed in the following table:
    Unless otherwise indicated, all the viscosity measurements of the inks were carried out with a rheometer, here a Bohlin® CVO® equipment, with a truncated conical rotor 50mm in diameter and at an angle of 4 °, and a peltier plane regulated at 20 ° C. Pre-shear at 100% for 10 seconds is applied before any measurement. Four or five points are measured per decade with 10s of measurement per point, starting with the highest gradients.
    PAA solutions with a molecular weight of 100,000 250,000 or 345,000g / mol have a low viscosity at 100% even at 12% concentrations. They do not include rheo-fluidifying character. These molecular weights correspond to the definition of PAAi, a molecular weight that achieves a high percentage of binder in the electrode without bringing too much viscosity to the electrode ink.
    PAA solutions with a molecular weight of 450,000 g / mol have a viscosity at 100% corresponding to that desired, but not a sufficient rheo-thinning character, even for a large concentration. This molecular weight does not correspond to any of the 2 PAA definitions.
    Solutions of PAA with a molecular weight of 1,250,000 or 3,000,000g / mol have a viscosity of 100%, provided that their content is low. They also have a rheo-fluidifying character compatible with that sought. These molecular weights correspond to the definition of PAA2, a molecular weight which makes it possible to give the electrode ink good rheological properties, but which does not make it possible to reach a large proportion of PAA in the ink.
    Two inks comprising only PAA with a molecular weight of less than 400,000g / mol have been developed. They were used to produce electrodes with a basis weight of about 5 mg of composite per cm 2 of electrode to be coated. The inks are the following: - Ink A: electrode composed of 90% of carbon and silicon composite having a specific capacity of 600mAh / g (this composite material is hereafter called composite gold SiC), 2% of carbon fibers , 3% ultra-divided carbon, 5% PAA molecular weight 250,000g / mol with a degree of dissociation of 33%, - Ink B: electrode composed of 90% composite, 2% carbon fiber, 3% ultra-divided carbon, 5% PAA molecular weight 250,000g / mol with a degree of dissociation of 100%.
    LiOH is used to dissociate the PAA in solution prior to incorporation into the ink.
    They are compared to three identical electrodes but where the binder is: - a PAA with a molecular weight of 450,000 g / mol of the CMC with a molecular weight of 250,000 g / mol a mixture of PAA and CMC with a molecular weight of 250,000 g / mol for the 2.
    These 3 inks are the following: - Ink C: electrode composed of 90% composite, 2% carbon fiber, 3% ultra-divided carbon, 5% PAA 450,000g / mol with a degree of dissociation of 33% - CMC ink: electrode composed of 90% composite, 2% carbon fiber, 3% ultra-divided carbon, 5% CMC 250,000g / mol with a degree of dissociation of 100% (CMC used is dissociated with carboxylate groups of sodium COONa), - CMC / PAA ink: electrode composed of 90% of composite, 2% of carbon fibers, 3% of ultra-divided carbon, 2.5% of CMC 250,000g / mol and 2 , 5% PAA 250,000g / mol with a degree of dissociation of 50% (CMC and PAA are dissociated with NaOH).
    The rheological properties of the five inks were measured, in viscosity, according to the protocol described previously, and in oscillation mode, at 25 ° C. and with the same geometry, but for a deformation of 1% between 0.1 and 10 Hz. points are measured by decade, with from 6 to 45s of measurement per point, without pre-shear, but with a rest of 10min.
    Figure 3a shows the viscosity of these inks as a function of shear. FIG. 3b shows the viscous and elastic modules obtained in oscillation mode, without significant deformation of the ink, in its linear domain, which gives access to the properties at rest of the ink.
    The viscosity curves (FIG. 3a) show that the inks A and C with PAAs of 250,000 g / mol and 450,000 g / mol, and a degree of dissociation of 33%, do not exhibit rheo-fluidizing character.
    This type of rheo-thinning behavior is achieved for mixtures with 5% PAA at 250,000 g / mol with a degree of dissociation of 100% (ink B). However, for ink B, between 0.1 and 1 s the viscosity sags and no longer tends towards infinite viscosity.
    CMC and CMC / PAA inks show this rheo-fluidizing behavior with, however, a ratio of less than 10 between 0.1 and 100% viscosities.
    Oscillation mode (Figure 3b), with module tracking, confirms these results. Whatever the frequency, there is always the viscous modulus G "which is greater than the elastic modulus G 'for the inks CMC, CMC / PAA, A, B and C. The ink does not block the movements of the particles. The ink is not stable at rest and is therefore not suitable for the conventional method of producing electrodes for Li-ion battery, by coating.
    Viscosity curves (FIGS. 4a and 4b) were also produced with the same components as before but with PAA mixtures: - Ink D: electrode composed of 90% of composite, 2% of carbon fibers, 3% of carbon ultra-divided, 1.5% PAA 1,250,000g / mol, 3,5% PAA 250,000g / mol with a degree of dissociation of 100% - Ink E: electrode composed of 90% of composite, 2% of fibers of carbon, 1.5% PAA 1,250,000g / mol, 3,5% PAA 250,000g / mol with a degree of dissociation of 100%, 3% of latex - Ink F: electrode composed of 90% of composite, 2% of carbon fiber, 2.5% PAA 1,250,000g / mol, 5.5% PAA 100,000g / mol with a degree of dissociation of 100% - Ink G: electrode composed of 90% composite, 2% fiber of carbon, 2.5% PAA 1,250,000g / mol, 5.5% PAA 250,000g / mol with a degree of dissociation of 100% - Ink H: electrode composed of 90% composite, 2% carbon fiber 2.5% PAA 1,250,000g / mol, 5.5% PA At 345,000g / mol with a degree of dissociation of 100% - Ink I: electrode composed of 90% composite, 2% carbon fiber, 0.5% PAA 3,000,000g / mol, 7,5% PAA 250,000 g / mol with a degree of dissociation of 100%
    The different inks evaluated based on PAA are summarized below:
    The carbon fibers are denoted CF, the ultra-divided carbon is denoted CD and the degree of dissociation is denoted DD.
    For inks D, E, F, G, H, and I additionally containing a high molecular weight PAA, with a degree of dissociation of 100%, the ink has a well-marked rheo-thinning character; a factor of at least 50 is observable between the viscosity at 100% and that at 0.1%.
    Another component, such as latex, can be added without altering the stability of the ink (ink E). At the module level, there is always an elastic modulus higher than the viscous modulus for low frequencies, characteristic of a stable ink at rest.
    The rheological evaluations of the different inks are grouped in the table below:
    The PAA alone mixtures referring to inks C and G were characterized by gel permeation chromatography (GPC). The mixtures were diluted to values of 0.1 mg / L to make the measurement. The results obtained reveal a mixture of molecular weights with a bi-modal type distribution.
    To integrate a large proportion of PAA and have both a viscosity at 100s' '' between 0.5 and 2Pa.s and a rheo-fluidifying character, it is necessary to have a mixture of PAA with two molecular weights distinct.
    The formulation based on a mixture of two polymers, the first polymer being a polyacrylate or a derivative thereof, the second polymer being a polyacrylate, a carboxymethylcellulose or a respective derivative thereof, makes it possible to produce negative electrodes having good properties electrochemical and mechanical, especially in terms of irreversible first cycle and loss per cycle cycling.
    The method for producing an electrode for a lithium battery or lithium battery comprises the following successive steps: depositing and drying an ink, as previously described, on a current collector, to obtain an electrode-drying of traces of solvent of the electrode, - calendering of the electrode.
    The drying process of the electrode is preferably carried out at a temperature below 150 ° C. and even more preferably at a temperature below 130 ° C.
    It is possible for the PAAs to cross-link with each other and for the electrode to comprise "macropolymers" PAA1-PAA1 PAA2-PAA2 or PAA1-PAA2, if the electrode is dried at a temperature higher than that conventionally used. For example, these are temperatures above 150 ° C. Nevertheless, this crosslinking reduces the elasticity of the binder and is undesirable for the performance of the electrode.
    It will advantageously be placed at temperatures below the temperatures indicated above so as to prevent the crosslinking of the polyacrylates.
    The binder is thus formed of a mixture of the first polyacrylate PAAi and the second polyacrylate PAA2, there is no crosslinking. The ink is initially obtained by mixing in distilled water, the various compounds: the electrochemically active material, the solvent, the binder, the electronically conductive agent, and optionally the additive.
    In addition, a base for dissociating the polymer may also be added to the ink. The ink may also include another component such as a polymer. The ink is then deposited as a layer of varying thickness on a generally metallic sheet constituting a current collector, to form an ink / collector assembly.
    The current collector is preferably of copper. This is, for example, a copper foil.
    The deposition of the ink is preferably carried out by a conventional coating method, for example with a controlled thickness transfer system or by a slot-shaped coating system. The electrode has a basis weight of at least 2.5 mg / cm 2 of deposited active material.
    Advantageously, the basis weight is at least 2.5 mg / cm 2 and is limited to 20 mg / cm 2. Preferably, the electrode has a basis weight ranging from 2.5 mg / cm 2 to 10 mg / cm 2 of deposited active material and a density of at least 1.4. The electrode obtained is thus compact and dense.
    Even more advantageously, the basis weight is between 4 and 10 mg / cm 2. The quality of the ink obtained makes it possible to produce a coating at a high coating speed of several m.sup.-1 ', adapted to an industrial application. The ink / collector assembly is then dried by any known method, to evaporate the solvent and obtain an electrode supported on the current collector.
    The electrodes obtained, with a basis weight of about Smg / cm 2 of active material, from such an ink have good mechanical properties, especially in terms of flexibility and adhesion, even without latex.
    These electrodes are easily integrated into Li-ion cells, generally by winding or stacking methods. The electrode is then dried by any known method, to evaporate the traces of solvent. The electrode thus formed may then be compressed or calendered in order to improve the energy density of the electrode and to increase the electronic conductivity of the electrode, typically to achieve a density of at least 1.4. . Compression or calendering has the effect of bringing the particles of electrochemically active material together, densifying the layer and thus improving the electrical percolation between the particles of the electrochemically active material of the electrode. The electrode for lithium accumulator, obtained by the method, comprises: an electrode active material, preferably based on silicon, a conductive agent, a binder.
    Silicon is in the form of nanoparticles. Silicon can be inserted into a micrometric matrix. Silicon is capable of forming an alloy with lithium LixSi type, with x between 0 and 3.75.
    Advantageously, 90% of the silicon in the form of nanoparticles has a size distribution of less than 300 nm, and preferably 50% of the silicon in the form of nanoparticles has a size distribution of less than 150 nm.
    The binder comprises a mixture of two polymers: the first polymer having a first molecular weight, the first polymer being a first polyacrylate or a derivative thereof, the second polymer having a second molecular weight, the second polymer being a second polyacrylate or a carboxymethyl cellulose, or a respective derivative thereof.
    The binder provides the mechanical strength, cohesion and flexibility of the electrode and improves the interaction between the electrode and the electrolyte of the lithium battery.
    The binder is, preferably, from 2% to 15% by weight of the electrode, and preferably from 4% to 10% by weight of the electrode.
    With such ranges, the electrochemical properties are improved.
    According to a first embodiment, the first polymer is a polyacrylate and the second polymer is a carboxymethyl cellulose.
    According to a second embodiment, the first polymer and the second polymer are polyacrylates or a derivative thereof.
    Preferably, the first polymer is a PAAi polyacrylate and the second polymer is a PAA2 polyacrylate.
    The first molecular weight is less than or equal to 400,000g / mol and greater than or equal to 150,000g / mol.
    The second molecular weight is greater than or equal to 650,000 g / mol and less than or equal to 4,000,000 g / mol, and preferably the second molecular weight is greater than or equal to 650,000 g / mol and less than or equal to 1,500,000 g / mol .
    The degree of dissociation of the polymers ranges from 35% to 100%.
    Even more preferentially, the first polymer is a PAAi polyacrylate and the second polymer is a PAA2 polyacrylate, the first molecular weight being greater than or equal to 250,000 g / mol and less than or equal to 400,000 g / mol, the second molecular weight being greater or equal to 1,000,000g / mol and less than or equal to 1,500,000g / mol, and the degree of dissociation of the polymers being greater than 90%.
    The first molecular weight is at most 67% by weight relative to the second molecular weight.
    Preferably, the binder consists of the two polymers.
    According to one embodiment, the lithium battery electrode, or lithium battery, consists of: the silicon-based electrode active material, the conductive agent, and the binder comprising the mixture of the two polymers. The electrode is advantageously devoid of latex.
    The mass percentage of the second polyacrylate is advantageously less than or equal to 2% relative to the total weight of the electrode to give a maximum ink viscosity of 5 Pa.s at 100 ° C. It is preferably greater than or equal to at 0.1% relative to the total weight of the electrode.
    It has also been found that there is no cracking and / or peeling off of the electrode for the selected PAA mixtures. The electrode has good homogeneity and good flexibility as well as good adhesion to the current collector. Lithium batteries having at least one such electrode have, therefore, improved electrochemical performance.
    The mechanical strength of the electrode makes it easy to print the electrode whatever the shape of the pattern, even for high electrode weights.
    The non-polymerization of PAAs during drying was verified. An electrode has undergone extraction treatment of the binder. This extracted binder was characterized by the chromatographic method described previously, making it possible to recover the bimodal distribution of the molecular mass.
    Cycling tests at 20 ° C. were also carried out on the electrodes prepared from the inks previously described, in a button cell facing lithium metal with a carbonate electrolyte containing fluorinated ethylene carbonate. The electrode is cycled at a rate of C / 10, a load in 10 hours taking into account the proportion and the specific capacity of the composite.
    The cycling is carried out with a VMP3 from Biology to have an accuracy of at least 0.05% in coulombic efficiency, the ratio between the delithiation or reduction current and the lithiation or oxidation current. for the same cycle (the cycle beginning with lithiation or reduction). The irreversible first cycle is thus equal to one minus the coulombic efficiency in the first cycle and the loss per cycle is equal to one minus the coulombic efficiency for a given cycle.
    The results showed that in the first cycle, the irreversible first cycle is important, associated with the formation of the electrode / electrolyte interface. Then, the loss per cycle decreases to stabilize completely after 10 cycles for several tens of cycles (Figure 5).
    The different electrodes tested are thus compared with respect to the irreversible first cycle and the stabilized loss after 10 cycles, typically between 10 and 20 cycles.
    The results are provided in the following tables:
    The worst performances (electrochemical and with respect to the quality of the electrode) are obtained by the electrodes consisting of a single binder of a single molecular weight.
    An improvement is obtained when using a binder comprising two polymers. And the best results are obtained with formulations D to I, which are PAA mixtures of two different molecular weights (with a first molecular weight of at most 67% relative to the second molecular weight) and a degree of dissociation of 100%.
    Results were also obtained in the 18650 reference format. The positive electrode is based on UC0O2, with a basis weight of 18.3 mg / cm 2, ie 2.5 mAh / cm 2, and a porosity of 25%. The two negative electrodes compared correspond to the CMC / PAA formulations and the mixture of two PAA (G electrode), with a basis weight of 5.6 mg / cm 2, ie 3.0 mAh / cm 2 and a porosity of 35%. The electrolyte is based on carbonates containing fluorinated ethylene carbonate. The following results were obtained for cycling at 20 ° C, at C / 2, between 4.2 and 2.7V:
    The capacity retention after a cycle number n is the ratio of the capacity discharged to cycle n and the capacity discharged to cycle 2.
    It has been observed that the PAA shows improved performances compared to a conventional formulation based on CMC.
    A reduction of 1.5% in the first cycle irreversible was observed between the element 18650 based on the electrode G in comparison with that with the electrode CMC / PAA.
    Capacity retention is also greatly improved with the 18650 element based on the G electrode compared to that with the CMC / PAA electrode.
    The life of the Li-ion battery with the optimized formulation at the negative electrode is increased by more than 50%, based on the number of cycles before reaching a capacity retention of 80% compared to the ability to cycle 2.
    权利要求:
    Claims (27)
    [1" id="c-fr-0001]
    claims
    An electrode for a lithium battery, or lithium battery, comprising: an electrode active material, based on silicon, a conductive agent, a binder, characterized in that the binder comprises a mixture of two polymers: The first polymer having a first molecular weight, the first polymer being a first polyacrylate or a derivative thereof, the second polymer having a second molecular weight, the second polymer being a second polyacrylate or a carboxymethyl cellulose, or a derivative thereof; respectively.
    [2" id="c-fr-0002]
    2. Electrode according to claim 1, characterized in that the first molecular weight is less than or equal to 400,000g / mol and greater than or equal to 150,000g / mol.
    [3" id="c-fr-0003]
    3. Electrode according to one of claims 1 and 2, characterized in that the second molecular weight is greater than or equal to 650,000g / mol and less than or equal to 4,000,000g / mol, and preferably the second molecular weight is greater than or equal to 650,000g / mol and less than or equal to 1,500,000g / mol.
    [4" id="c-fr-0004]
    4. Electrode according to one of claims 1 to 3, characterized in that the degree of dissociation of the polymers ranges from 35% to 100%.
    [5" id="c-fr-0005]
    5. Electrode according to any one of claims 1 to 4, characterized in that the first polymer is a polyacrylate and in that the second polymer is a carboxymethyl cellulose.
    [6" id="c-fr-0006]
    6. Electrode according to any one of claims 1 to 4, characterized in that the first polymer and the second polymer are polyacrylates or a derivative thereof.
    [7" id="c-fr-0007]
    7. Electrode according to claim 6, characterized in that the first polymer and the second polymer are polyacrylates.
    [8" id="c-fr-0008]
    8. Electrode according to claim 7, characterized in that: - the first molecular weight is greater than or equal to 250,000g / mol and less than or equal to 400,000g / mol, - the second molecular weight is greater than or equal to 1,000,000g / mol and less than or equal to 1,500,000g / mol, the degree of dissociation of the polymers is greater than 90%.
    [9" id="c-fr-0009]
    9. Electrode according to any one of claims 1 to 8, characterized in that the first molecular weight is at most 67% by mass relative to the second molecular weight.
    [10" id="c-fr-0010]
    10. Electrode according to one of claims 1 to 9, characterized in that the binder consists of the two polymers.
    [11" id="c-fr-0011]
    11. Electrode according to any one of the preceding claims, characterized in that the binder is from 2% to 15% of the weight of the electrode, and preferably from 4% to 10% of the weight of the electrode.
    [12" id="c-fr-0012]
    12. Electrode according to any one of the preceding claims, characterized in that the silicon is in the form of nanoparticles, and the silicon being capable of forming an alloy with LixSi-type lithium, with X ranging from 0 to 3.75. .
    [13" id="c-fr-0013]
    13. Electrode according to any one of the preceding claims, characterized in that the silicon is inserted into a micrometric matrix, and in that the silicon is capable of forming an alloy with the type □ xSi lithium, with x between 0 and 3.75.
    [14" id="c-fr-0014]
    14. An electrode according to claim 12 or 13, characterized in that 90% of the silicon in the form of nanoparticles has a size distribution of less than 300 nm, and preferably 50% of the silicon in the form of nanoparticles has a smaller size distribution. at 150nm.
    [15" id="c-fr-0015]
    15. Electrode according to any one of the preceding claims, characterized in that it has a basis weight ranging from 2.5 mg / cm 2 to 10 mg / cm 2 of deposited active material and a density of at least 1.4.
    [16" id="c-fr-0016]
    16. Electrode according to any one of claims 1 to 15, characterized in that it is devoid of latex.
    [17" id="c-fr-0017]
    17. An electrode according to any one of claims 1 to 15, characterized in that the electrode further comprises an additive, such as carboxymethyl cellulose, latex, a crosslinking agent or a polyacrylate of another molecular weight. the additive is 5% by weight or less of the electrode, and preferably 3% or less.
    [18" id="c-fr-0018]
    18. Electrode according to any one of claims 1 to 16, characterized in that it consists of: - the electrode active material, based on silicon, - the conductive agent, - the binder comprising the mixture of two polymers: the first polymer having a first molecular weight, the first polymer being a first polyacrylate or a derivative thereof. ο the second polymer having a second molecular weight, the second polymer being a second polyacrylate or a carboxymethyl cellulose, or a respective derivative thereof.
    [19" id="c-fr-0019]
    Ink for producing a lithium ion battery electrode according to any one of claims 1 to 18, comprising: an electrode active material, based on silicon, a solvent, a conductive agent, a binder, characterized in that the binder comprises a mixture of two polymers; The first polymer having a first molecular weight, the first polymer being a first polyacrylate or a derivative thereof, the second polymer having a second molecular weight, the second polymer being a second polyacrylate or a carboxymethyl cellulose, or a derivative thereof; respectively.
    [20" id="c-fr-0020]
    20. Ink according to claim 19, characterized in that the first molecular weight is less than or equal to 400,000g / mol and greater than or equal to 150,000g / mol.
    [21" id="c-fr-0021]
    21. Ink according to one of claims 19 and 20, characterized in that the second molecular weight is greater than or equal to 650,000g / mol and less than or equal to 4,000,000g / mol, and preferably the second molecular weight is greater than or equal to 650,000g / mol and less than or equal to 1,500,000g / mol.
    [22" id="c-fr-0022]
    22. Ink according to any one of claims 19 to 21, characterized in that the degree of dissociation of the polymers ranges from 35% to 100%.
    [23" id="c-fr-0023]
    Ink according to any one of claims 19 to 22, characterized in that the first polymer and the second polymer are polyacrylates.
    [24" id="c-fr-0024]
    Ink according to any one of claims 19 to 22, characterized in that the first polymer is a polyacrylate and in that the second polymer is a carboxymethyl cellulose.
    [25" id="c-fr-0025]
    25. Ink according to any one of claims 19 to 24, characterized in that the binder represents from 2% to 15% by weight of the dry extract, and preferably from 4% to 10% by weight of the dry extract.
    [26" id="c-fr-0026]
    Ink according to any one of Claims 19 to 25, characterized in that the silicon is in the form of nanoparticles, the silicon being included or not in a micrometric matrix, and being capable of forming an alloy with lithium of the type. LixSi, with x between 0 and 3.75.
    [27" id="c-fr-0027]
    Ink according to the preceding claim, characterized in that 90% of the silicon in the form of nanoparticles has a size distribution of less than 300 nm, and preferably 50% of the silicon in the form of nanoparticles has a size distribution of less than 150 nm. .
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    同族专利:
    公开号 | 公开日
    US11050054B2|2021-06-29|
    WO2017153678A1|2017-09-14|
    EP3427318A1|2019-01-16|
    EP3427318B1|2021-04-21|
    JP2019509596A|2019-04-04|
    PL3427318T3|2021-12-13|
    CN109379899A|2019-02-22|
    KR20190008835A|2019-01-25|
    US20200343542A1|2020-10-29|
    HUE055302T2|2021-11-29|
    FR3048821B1|2021-12-17|
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    法律状态:
    2017-03-31| PLFP| Fee payment|Year of fee payment: 2 |
    2017-09-15| PLSC| Publication of the preliminary search report|Effective date: 20170915 |
    2018-03-29| PLFP| Fee payment|Year of fee payment: 3 |
    2020-03-31| PLFP| Fee payment|Year of fee payment: 5 |
    2021-03-30| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1651917A|FR3048821B1|2016-03-08|2016-03-08|INK INCLUDING A MIXTURE OF POLYACRYLIC ACIDS FOR THE REALIZATION OF A LITHIUM-ION BATTERY ELECTRODE, AND ELECTRODE OBTAINED WITH SUCH AN INK|FR1651917A| FR3048821B1|2016-03-08|2016-03-08|INK INCLUDING A MIXTURE OF POLYACRYLIC ACIDS FOR THE REALIZATION OF A LITHIUM-ION BATTERY ELECTRODE, AND ELECTRODE OBTAINED WITH SUCH AN INK|
    JP2018547401A| JP2019509596A|2016-03-08|2017-03-07|A lithium ion battery comprising a binder comprising a first polymer that is one of a first polyacrylate or a derivative thereof and a second polymer that is a second polyacrylate or a carboxymethylcellulose or one of derivatives thereof. Electrode and ink for producing the electrode|
    CN201780023961.6A| CN109379899A|2016-03-08|2017-03-07|Lithium ion battery electrode including the adhesive formed by the blend of two kinds of polymer, first polymer is one of first polyacrylate or derivatives thereof, second polymer is one of the second polyacrylate or carboxymethyl cellulose or derivatives thereof, for manufacturing the ink of the electrode|
    EP17713734.6A| EP3427318B1|2016-03-08|2017-03-07|Electrode for lithium-ion battery comprising a binder formed from a blend of two polymers, the first polymer being a first polyacrylate or one of its derivatives, the second polymer being a second polyacrylate or a carboxymethyl cellulose or one of their derivatives, ink for producing such an electrode.|
    KR1020187028556A| KR20190008835A|2016-03-08|2017-03-07|An electrode for a lithium-ion battery comprising a binder formed from a blend of two polymers, a first polymer which is one of a first polyacrylate or a derivative thereof, a second polyacrylate or a second polymer which is one of carboxymethylcellulose or derivatives thereof, Ink for producing such an electrode|
    PCT/FR2017/050507| WO2017153678A1|2016-03-08|2017-03-07|Electrode for lithium-ion battery comprising a binder formed from a blend of two polymers, the first polymer being a first polyacrylate or one of its derivatives, the second polymer being a second polyacrylate or a carboxymethyl cellulose or one of their derivatives, ink for producing such an electrode.|
    US16/083,828| US11050054B2|2016-03-08|2017-03-07|Electrode for lithium-ion battery comprising a binder formed from a blend of two polymers, the first polymer being a first polyacrylate or one of its derivatives, the second polymer being a second polyacrylate or a carboxymethyl cellulose or one of their derivatives, ink for producing such an electrode|
    HUE17713734A| HUE055302T2|2016-03-08|2017-03-07|Electrode for lithium-ion battery comprising a binder formed from a blend of two polymers, the first polymer being a first polyacrylate or one of its derivatives, the second polymer being a second polyacrylate or a carboxymethyl cellulose or one of their derivatives, ink for producing such an electrode.|
    PL17713734T| PL3427318T3|2016-03-08|2017-03-07|Electrode for lithium-ion battery comprising a binder formed from a blend of two polymers, the first polymer being a first polyacrylate or one of its derivatives, the second polymer being a second polyacrylate or a carboxymethyl cellulose or one of their derivatives, ink for producing such an electrode.|
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