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    • 专利摘要:
    A method of manufacturing a fully solid thin-film battery comprising the following successive steps: a) depositing a layer comprising at least one anode material on its conductive substrate; b) depositing a layer comprising at least one cathode material on its conductive substrate; c) depositing on at least one layer obtained in step a) and / or b) a layer comprising at least one solid electrolyte material comprising a crosslinked solid polymer material comprising ionic groups; d) successively face-face stacking: - either a layer of anode material coated with a layer of solid electrolyte material obtained in step c) with a layer of cathode material coated or not with a layer solid electrolyte material obtained in step c); or a layer of cathode material coated with a layer of solid electrolyte material obtained in step c) with a layer of anode material coated or not with a layer of solid electrolyte material obtained at step c); e) thermal treatment and / or mechanical compression of the stack obtained in step d) is performed to obtain a fully solid thin-film battery.
    公开号:FR3023418A1
    申请号:FR1456273
    申请日:2014-07-01
    公开日:2016-01-08
    发明作者:Fabien Gaben
    申请人:I TEN；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of batteries. It relates more particularly to fully solid batteries, and a new method of manufacturing such batteries. STATE OF THE ART Batteries are known comprising electrolytes consisting either of a salt dissolved in a dry polymer or of a polymer swollen or gelled by a solution of a salt in a mixture of aprotic polar organic solvents. Typically, the production of the electrolyte consists in dissolving a polymer, a salt and a mixture of solvents constituting the polymer electrolyte, then, after having deposited the mixture in the form of a film, the solvent is removed at atmospheric pressure or reduced without removing the constituent solvents of the polymer electrolyte. WO 98/35397 A1 discloses a battery comprising an electrolyte formed from a dried electrolyte solution comprising an amorphous thermoplastic polyimide soluble in an organic solvent, and a lithium salt. However, the use of organic solvent does not guarantee the safety and the life of the battery by protecting against the risk of short circuit and solvent ignition. Also known are "all solid" batteries comprising solid electrolytes made from polyethylene oxide (PEO) or polypropylene oxide (PPO) -based polymer material. However, these types of electrolytes have relatively low ionic conductivity at room temperature (of the order of 10-7 S / cm). US 5,407,593 teaches that ion transport in a polymer electrolyte passes through the amorphous region of a polymer matrix. Thus, the ionic conductivity of a polymer electrolyte can be increased by decreasing the crystalline region and increasing the amorphous region of the polymer. Also, it is possible by changing the glass transition temperature of the polymer, by removing the crystalline areas and using lower molecular weights, to increase the ionic conduction. However, these modifications on the polymer material often create a strong degradation of the mechanical properties of the electrolyte.
    [0002] Moreover, it has been shown that the crosslinking of conductive polymer can increase the strength of the films, but this results in a decrease in the conductivity. For example, the article by P.M. Blonsky and D. F. Shriver, J. Am. Chem. Soc. 1984, 106, pages 6854-6855 discloses a poly (bis (methoxyethoxy) phosphazene) polymer comprising short chains of polyethylene oxide whose ionic conductivity at 25 ° C exceeds 10-5 S / cm. However, the electrochemical stability of crosslinked solid polymer material as well as its mechanical properties are limited. The object of the present invention is to provide an all-solid battery comprising a solid electrolyte of crosslinked polymer material, having good mechanical strength and having an ionic conductivity greater than that of the solid electrolytes made of crosslinked polymer material known from the state of the art. Another object of the invention is to manufacture batteries in thin layers by a process that can be implemented industrially in a fairly simple manner. OBJECTS OF THE INVENTION A first object of the invention relates to a method of manufacturing a fully solid thin-film battery comprising the following successive steps: a) depositing a layer comprising at least one anode material (here called " layer of anode material ") on its conductive substrate, preferably selected from the group consisting of a metal sheet, a metal strip, a metallized insulating sheet, a metallized insulating strip, a metallized insulating film, said conductive substrates, or their conductive elements, which can serve as anode current collector; b) depositing a layer comprising at least one cathode material (here called "layer of cathode material") on its conductive substrate, preferably selected from the group consisting of a metal sheet, a metal strip, a metallized insulating sheet, a metallized insulating strip, a metallized insulating film, said conductive substrates, or their conductive elements, being able to serve as a cathode current collector, it being understood that the steps a) and b) can be reversed; c) depositing on at least one layer obtained in step a) and / or b) a layer comprising at least one solid electrolyte material (here called "layer of electrolyte material") comprising a crosslinked solid polymer material having ionic groups; d) successively face-face stacking: - either a layer of anode material coated with a layer of solid electrolyte material obtained in step c) with a layer of cathode material coated or not with a layer solid electrolyte material obtained in step c); a layer of cathode material coated with a layer of solid electrolyte material obtained in step c) with a layer of anode material coated or not with a layer of solid electrolyte material obtained from step c); e) thermal treatment and / or mechanical compression of the stack obtained in step d) is performed to obtain a fully solid thin-film battery.
    [0003] Preferably, the crosslinked solid polymer material is selected from polymethyl methacrylates, polyamines, polyimides, or polysiloxanes. Preferably, the ionic groups are chosen from the following cations: imidazolium, pyrazolium, tetrazolium, pyridinium and pyrrolidinium, such as n-propyl-n-methylpyrrolidinium (also known as PYR13) or n-butyl-n-methylpyrrolidinium. (also known as PYR14), ammonium, phosphonium or sulfonium; and / or among the following anions: bis (trifluoromethane) sulfonimide, bis (fluorosulfonyl) imide, or n (nonafluorobutanesulfonyl) -n- (trifluoromethanesulfonyl) imide. In a particular embodiment of the process according to the invention, the crosslinked solid polymer material is obtained by a step of polymerizing a mixture of monomers and / or oligomers and / or pre-polymers comprising one or more groups that can be polymerized thermally. or photochemical, said mixture of monomers and / or oligomers and / or pre-polymers comprising one or more reactive groups for grafting said ionic groups, and then drying the crosslinked polymer material obtained.
    [0004] Advantageously, the thermal and / or photochemical polymerization is carried out directly on the layer (s) of anodes and / or cathodes. The crosslinked polymer material comprising ionic groups deposited in step c) is produced from at least one of the following techniques: dipcoating, spin-coating, roll coating coating), doctor blade, electrospray, or electrophoresis. The thickness of the electrolyte layer c) is less than 10 μm, preferably less than 5 μm, and even more preferably less than 2 μm. The layers of anode, cathode and solid electrolytes are deposited among at least one of the following techniques: (i) physical vapor deposition (PVD), and more particularly by evaporation in vacuo, by laser ablation, by ion beam, by sputtering; (ii) chemical vapor deposition (CVD), and more particularly plasma assisted (PECVD), laser assisted (LACVD), or aerosol assisted (AA-CVD); (iii) electrospray; (iv) electrophoresis; (v) aerosol deposition; (vi) sol-gel; (vii) soaking, more particularly by dip-coating, spin-coating, or by the Langmuir-Blodgett process.
    [0005] Preferably, the anode, cathode and electrolyte layers are deposited by electrospray, electrophoresis, aerosol deposition, dipping, and are preferably all electrophoretically deposited. Advantageously, the layers of anode material and / or cathode further comprise electronically conductive materials, and in particular graphite, and / or lithium ion conductive materials, of the type used to produce the electrolyte films. . In a particular embodiment, the anode and / or cathode layers are produced by deposition of nanoparticles respectively anode material, cathode among at least one of the following techniques: electrospray, electrophoresis, aerosol deposition, soaking. Preferably, the layers of anode material, cathode and electrolyte are all electrophoretically deposited. Advantageously, the heat treatment is carried out at a temperature of between 50 ° C. and 300 ° C., preferably between 100 ° C. and 200 ° C. and / or in that the mechanical compression of the layers to be assembled is carried out at a pressure between 10 and 100 MPa, preferably between 20 and 50 MPa. The anode material layer a) is made from material chosen from: (i) tin oxynitrides (of typical formula SnOxNy); (ii) lithium iron phosphate (of typical formula LiFePO4); (iii) mixed oxynitrides of silicon and tin (of typical formula SiaSnbOyNz with a> 0, b> 0, a + LK2, 0 <z3) (also called SiOn), and in particular SiSno, 8701,2N1,72; as well as oxynitrides in the form SiaSnbCcOyNz with a> 0, b> 0, a-FLK2, 0 <c <10, 0 <y <24, 0 <z <17; SiaSnbCcOyNzX, and SiaSnbOyNzXn with Xn at least one of F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb; (iv) the nitrides of the type SixNy (in particular with x = 3 and y = 4), SnxNy (in particular with x = 3 and y = 4), ZnxNy (in particular with x = 3 and y = 4), Li3_xMxN (with M = Co, Ni, Cu); (v) the oxides SnO2, Li4Ti5012, SnBo, 6P0, 402.9.
    [0006] The cathode material layer b) is made from cathode material selected from: (i) LiMn 2 O 4, LiCoO 2, LiNiO 2, LiMn 1.5 TiO, 504, LiMn 1.5Ni 0.5 O xXx O 4 (where x is selected from Al, Fe , Cr, Co, Rh, Nd, other rare earths, and where 0 <x <0.1), LiFeO2, LiMn1i3Ni1i3C01 / 304; (ii) LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2 (PO4) 3 phosphates; phosphates of formula LiMM'PO4, with M and M '(M # M') selected from Fe, Mn, Ni, Co, V; (iii) all the lithiated forms of the following chalcogenides: V205, V308, TiS2, titanium oxysulfides (TiOyS), tungsten oxysulfides (VVOyS), CuS, CuS2. In a particular embodiment, the method further comprises a step f) of encapsulation of the battery obtained in step e) by deposition of at least one encapsulating layer of ceramic material, vitreous or glass-ceramic. Advantageously, anodic and cathodic terminations are carried out by metallization of the cut sections, preferably by deposition of a layer of tin optionally deposited on a first sub-layer of nickel and / or epoxy resin loaded with metal particles.
    [0007] Preferably, the conductive substrates are made of aluminum, copper or nickel, preferably nickel, and optionally coated with a noble metal selected from the following metals: gold, platinum, palladium, vanadium, cobalt , nickel, manganese, niobium, tantalum, chromium, molybdenum, titanium, palladium, zirconium, tungsten or any alloy comprising at least one of these metals.
    [0008] Another object of the invention relates to a battery that can be obtained by the method according to the invention. Advantageously, the surface capacitance of the cathode is greater than or equal to the surface capacitance of the anode. In a preferred embodiment, the stack of cathode and anode layers is shifted laterally. Advantageously, the battery comprises at least one encapsulation layer, preferably a ceramic, glass or glass-ceramic layer. Even more advantageously, the battery comprises a second encapsulation layer deposited on said first encapsulation layer, said second encapsulation layer preferably being silicone. Preferably, said at least one encapsulation layer completely covers four of the six faces of said battery and partially the two remaining faces, located under the metallizations used for the connection of the battery. In a particular embodiment, the battery comprises terminations at the level where the cathode current collectors, respectively anodic, are apparent. Advantageously, the anode connections and the cathode connections are on the opposite sides of the stack.
    [0009] According to a particular aspect of the invention, the battery is entirely inorganic. DETAILED DESCRIPTION OF THE INVENTION 1. Definitions In the context of the present invention, the term "electrophoretic deposition" or "electrophoretic deposition" means a layer deposited by a process for deposition of particles previously suspended in a liquid medium, on a preferably conductive substrate, the displacement of the particles towards the surface of the substrate being generated by the application of an electric field between two electrodes placed in the suspension, one of the electrodes constituting the conductive substrate on which the deposit is made, the other electrode ("counter-electrode") being placed in the liquid phase. A so-called "dense" deposit of particles is formed on the substrate, if the zeta potential of the suspension of the particles has an appropriate value, and / or following a specific densification treatment of thermal and / or mechanical nature. This deposit has a particular structure and recognizable by the skilled person that distinguishes it from the deposits obtained by any other technique. For the purpose of this paper, the size of a particle is its largest dimension. Thus, a "nanoparticle" is a particle of which at least one of the dimensions is less than 100 nm. The "particle size" or "average particle size" of a powder or set of particles is given in D50.
    [0010] Battery means "any solid" (also called here battery "fully solid"), a battery does not include liquid phase material. The term "surface capacitance" of an electrode is the amount of lithium ion that can be inserted into an electrode (expressed in mA.h / cm 2). 2. Detailed Description In order to meet the drawbacks mentioned above, the inventor has developed a new process for manufacturing all-solid batteries that do not contain organic solvents so that they can be heated without risk of combustion. The objectives are achieved by carrying out a method of manufacturing a thin-film battery comprising a solid electrolyte comprising at least one crosslinked polymer material comprising ionic groups. The batteries obtained by the process according to the invention are of multilayer structure, in opposition to planar structures of conventional thin-layer batteries, in order to obtain batteries having a good density of energy and power. In addition, the method of obtaining these batteries makes it possible to assemble the layers of the battery at a relatively low temperature, ie at a temperature below 300 ° C., without reducing the surface capacitances of the electrodes constituting the battery. resultant. The realization of a "all solid" battery requires the use of dimensionally stable materials, in order to make the behavior of the battery more reliable, particularly as regards the limitation of deformation stresses on the encapsulation, or on the electrodes. The anode and cathode layers are deposited among at least one of the following techniques: i) Physical vapor deposition (PVD), and more particularly by evaporation under vacuum, by laser ablation, by ion beam, by sputtering; ii) chemical vapor deposition (CVD), and more particularly plasma assisted (PECVD), laser assisted (LACVD), or aerosol assisted (AA-CVD); iii) electrospray; iv) electrophoresis; v) aerosol deposition; vi) sol-gel; vii) soaking, more particularly by dip-coating, spin-coating, or by the Langmuir-Blodgett process. According to the invention, the anode and cathode layers are advantageously deposited by electrophoresis. The electrophoretic deposition of particles is done by the application of an electric field between the substrate on which the deposit is made and a counterelectrode, allowing the particles charged with the colloidal suspension to move, and to deposit them on the substrate. The absence of binders and other solvents deposited on the surface with the particles makes it possible to obtain very compact deposits. The compactness obtained thanks to the electrophoretic deposition limits or even avoids the risk of cracks or appearance of other defects in the deposit during the drying steps. In addition, the deposition rate can be very high depending on the applied electric field and the electrophoretic mobility of the particles of the suspension. According to the invention, the method of manufacturing an all-solid battery according to the invention comprises a step a) of depositing a layer of anode materials. The materials chosen for the layer of anode material are preferably selected from the following materials: (i) tin oxynitrides (of typical formula SnOxNy); (ii) lithium iron phosphate (of typical formula LiFePO4); (iii) mixed oxynitrides of silicon and tin (of typical formula SiaSnbOyNz with a> 0, b> 0, a-FLK2, 0 <y4, 0 <z3) (also known as SiTON), and in particular SiSno, 8701, 2N, 1.72; as well as oxynitrides in the form SiaSnbCcOyNz with a> 0, b> 0, a-FLK2, 0 <c-10, 0 <y <24, 0 <z <17; SiaSnbCcOyNzX, and SiaSnbOyNzXa with Xn at least one of F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb. (Iv) SixNy nitrides (especially with x = 3 and y = 4), SnxNy (in particular with x = 3 and y = 4), ZnxNy (in particular with x = 3 and y = 4), Li3_xMxN (with M = Co, Ni, Cu); (v) the oxides SnO2, Li4Ti5012, SnBo, 6P0, 402.9. Li4Ti5O12 for the production of an anode layer is more particularly preferred.
    [0011] In addition, Li4Ti5O12 is a lithium insertion material reversibly inserting lithium ions without inducing deformation of the host material. According to the invention, the method of manufacturing an all-solid battery comprises a step b) of depositing a layer of cathode materials. The cathode material layer is preferably made by electrophoresis. The materials chosen for the anode material layer are preferably selected from the following materials: (i) LiMn 2 O 4, LiCoO 2, LiNiO 2, LiMn 1.5 TiO, 504, LiMn 1.5Ni 0.5 O xXx O 4 oxides (where X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earths, and where 0 <x <0.1), LiFeO2, LiMn113Ni113C01 / 304; (ii) LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2 (PO4) 3 phosphates; (iii) all lithiated forms of the following chalcogenides: V205, V308, TiS2, titanium oxysulfides (TiOySz), tungsten oxysulfides (VVOySz), CuS, CuS2.
    [0012] Advantageously, the deposits of the layer of anode material and cathode are made by electrophoretic deposition of nanoparticles of anode material and cathode respectively.
    [0013] The cathode electrode, consisting of a LiMn 2 O 4 thin film deposited on a metal substrate, preferably nickel, is advantageously produced without resorting to vacuum techniques or dry rooms, which are very expensive equipment to implement. . Indeed, LiMn2O4, such as LiMn1,5Ni0,504 are not spontaneously sensitive to air, however it is recommended to avoid prolonged exposure.
    [0014] The impact of exposures of cathode materials to the air during the manufacture of the electrodes remains negligible compared to the relatively short implementation times. For the production of the anode or the cathode, it is possible to add nanoparticles of electronically conductive materials, and in particular graphite, and / or ionic conductive materials, of the type used to make the films, to the materials mentioned above. electrolyte (described below). Advantageously, the deposits of the layer of anode material and cathode are made directly on their metal substrate. For small nanoparticle sizes, i.e. less than 100 nm, deposition of the anode, cathode and electrolyte layers are achieved by electrospray, electrophoresis, aerosol deposition, or dipping. Advantageously, the anode, cathode and electrolyte layers are all deposited by electrophoresis. This particular embodiment of the method according to the invention makes it possible to obtain a dense and compact layer of nanoparticles, in particular by self-densification (called "self-sintering") of the nanoparticle layer during the electrophoretic deposition step, drying and / or heat treatment at low temperature. Moreover, the electrophoretic deposition of the layer of anode material or cathode being compact, the risk of cracking of the layer after drying is reduced, and this, unlike nanoparticle layers made from inks or fluids, having low solids and for which the deposits contain a large amount of solvent, which after drying gives rise to cracks in the deposit which is detrimental to the operation of a battery. According to the invention, the deposition of the layer of anode material or cathode is carried out directly on its conductive substrate, preferably a metal conductive substrate selected from the following materials: nickel, aluminum or copper. In a preferred embodiment, the deposition of the anode material or cathode layer is performed on a nickel substrate. The thickness of the substrate is less than 10 μm, preferably less than 5 μm. The conductive substrates may be made in the form of sheets, possibly sheets comprising the patterns of the pre-cut electrodes or in the form of strips. In order to improve the quality of the electrical contacts with the electrodes, the substrates may advantageously be coated with a metal or a metal alloy, preferably chosen from gold, chromium, stainless steel, palladium, molybdenum, titanium, tantalum, or silver.
    [0015] According to the invention, the deposition of a layer of nanoparticles of anode material or of cathode directly on its conducting substrate, for example by electrophoresis, makes it possible to obtain a dense layer of nanocrystalline structure. However, the formation of grain boundaries is possible, leading to the formation of a particular layer of structure, between that of an amorphous and crystallized material, which can in certain cases limit the diffusion kinetics of the lithium ions in the thickness of the electrode. Thus, the power of the battery electrode and the life cycle can be affected. Advantageously, in order to improve the performance of the battery, a recrystallization heat treatment may be performed to improve the crystallinity, and possibly the consolidation of the electrode to enhance the power of the electrodes (anode and / or cathode). The recrystallization heat treatment of the anode and / or cathode layer is carried out at a temperature of between 300 ° C. and 1000 ° C., preferably between 400 ° C. and 800 ° C., and even more preferentially between 500 ° C. and 700 ° C. The heat treatment must be performed after step a) and / or b) deposition of the anode layer and / or cathode, but before step c) of deposition of the electrolyte layer. According to the invention, the method of manufacturing a battery comprises a step c) of depositing a solid electrolyte layer comprising at least one crosslinked solid polymer material comprising ionic groups. The deposition of the electrolyte material layer is performed on the anode material layer and / or on the cathode material layer.
    [0016] Preferably, the ionic groups are chosen from the following cations: imidazolium, pyrazolium, tetrazolium, pyridinium, pyrrolidinium, such as n-propyl-n-methylpyrrolidinium (also called PYR13) or n-butyl-n methylpyrrolidinium (also known as PYR14), ammonium, phosphonium or sulfonium; and / or among the following anions: bis (trifluoromethane) sulfonimide, bis (fluorosulfonyl) imide, or n (nonafluorobutanesulfonyl) -n- (trifluoromethanesulfonyl) imide (of empirical formula C5F12NO4S2, also called IM14). The use of such anions makes it possible to retain good properties of resistance to exposure to air and moisture, which simplifies industrial implementation and guarantees better performance in terms of battery life. . In addition, the layer of crosslinked solid polymer material comprising ionic groups makes it possible to guarantee the safety and the service life of the battery by protecting it against the risks of short circuit and solvent ignition. Indeed, these polymeric materials are completely solid and do not include any liquid electrolyte, or dissolved in a solvent. In addition, these crosslinked solid polymer materials are resistant to high temperatures, without the risk of evaporation or inflammation of an organic solvent.
    [0017] Also, these solid electrolytes being more resistive than liquid electrolytes based on aprotic solvents containing lithium salts, it is necessary to make thin films if we want to have sufficiently powerful batteries. Thus, the thickness of the electrolyte layer c) is less than 10 μm, preferably less than 5 μm, and even more preferably less than 2 μm.
    [0018] In one embodiment of the process according to the invention, the crosslinked solid polymer material containing ionic groups is deposited directly by dip-coating, spin-coating, roll-coating. ), doctor blade, electrospray, or electrophoresis. For this purpose, the polymer material is first dissolved in a suitable solvent, the dissolved polymer material is deposited on the layer (s) of the anode, cathode and / or electrolyte and then the layer of material is dried. polymer to remove the solvent. Advantageously, the deposition of the crosslinked solid polymer material is carried out by electrophoresis in order to limit the defects in the layer which could lead to short circuits on the final battery. Moreover, the electrophoretic deposition makes it possible to reduce the risk of cracking of the layer after drying, and this, unlike layers made from inks or fluids, having low solids and for which the deposits contain solvent in large amounts. quantity, which after drying gives rise to the appearance of cracks in the deposit, detrimental to the operation of a battery.
    [0019] In another embodiment of the process according to the invention, a monomer and / or an oligomer and / or a prepolymer comprising one or more polymerizable groups are deposited on the layer of anode and / or cathode material. Preferably, a prepolymer is deposited comprising one or more reactive groups allowing the grafting of the ionic groups. The polymerization is carried out thermally and / or photochemically directly on the layer (s) of anode and / or cathode. Typically, the polymerization is carried out in the presence of a thermal initiator, for example selected from benzoyl peroxide, acetyl peroxide or azoisobutyronitrile, and / or a photochemical initiator, for example selected from benzoin, an acetophenone such as 2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxyacetophenone. The deposition of a crosslinked solid polymer material comprising ionic groups makes it possible to considerably increase the ionic conductivity of the electrolyte. In addition, these materials are difficult to ignite, resistant to high temperature, and have negligible vapor pressure. The layer of crosslinked polymer material comprising ionic groups then makes it possible to manufacture a battery in thin layers of three-dimensional structure without resorting to a heat treatment and / or a severe mechanical compression during the step of assembling said battery .
    [0020] Indeed, the production of at least one layer of crosslinked solid polymer material comprising ionic groups makes it possible to assemble the electrodes at a low temperature, ie a temperature not exceeding 300 ° C., preferably 200 ° C. and even more preferably 150 ° C.
    [0021] According to a particular embodiment of the method of the invention, the electrodes (anode and cathode) are "punched" in a cutting pattern to make cuts to the dimensions of the battery to achieve. In a particular embodiment, the punching of the electrodes may be performed after step c) of depositing the electrolyte layer of crosslinked solid polymer material comprising ionic groups. These patterns comprise three cutouts which are adjacent (for example U-shaped) and which define the size of the battery. A second slot can be made on the uncut side to be able to ensure the passage of products necessary for the encapsulation of the component. The anode and cathode electrodes are then stacked alternately to constitute a stack of several elementary cells. The cutting patterns of the anodes and cathodes are placed in "head-to-tail" configuration.
    [0022] In another particular embodiment of the method according to the invention, the electrodes are cut before step c) of deposition of the electrolyte layer (s) of crosslinked solid polymer material comprising ionic groups, allowing the recovery electrode edges by an electrolyte film, thereby protecting the contact of the electrodes with the atmosphere, and improving the calendar life of the battery. In an alternative embodiment, the cuts are made on the substrates before the steps a) and b) of depositing the anode and cathode layer, allowing the edges of the electrodes to be covered by an electrolyte film made of material crosslinked solid polymer having ionic groups. This particular embodiment has the advantage of covering the electrode edges before the deposition of the layer of electrolyte material, which subsequently makes it possible to easily produce an encapsulation film around the electrodes, especially when the layer Electrolyte is composed of moisture-stable materials. The overlapping of the lateral edges of the electrodes also makes it possible to reduce the risk of short circuit in the cell.
    [0023] Finally, an essential step of the method according to the invention comprises a heat treatment and / or mechanical compression of the stack obtained previously to obtain a fully solid thin-film battery. The heat treatment is carried out at a temperature of between 50 and 300 ° C., preferably 100 and 200 ° C. Advantageously, the temperature of the heat treatment does not exceed 200 ° C. Advantageously, the mechanical compression of the layers to be assembled is carried out at a pressure of between 10 and 100 MPa, preferably between 20 and 50 MPa. In a particular embodiment, it is advantageous, after the stacking step and before the addition of the terminations, to encapsulate the stack by depositing a thin layer of encapsulation to ensure the protection of the cell of the battery. vis-à-vis the atmosphere. The encapsulation layer must be chemically stable, withstand high temperature and be impermeable to the atmosphere to play its barrier layer function. For example, the thin encapsulation layer consists of either a polymer, or a ceramic, glass or glass ceramic, which may be for example in the form of oxide, nitride, phosphates, oxynitride, or of siloxane. Advantageously, this encapsulation layer comprises a ceramic, glass or glass-ceramic layer coated with an epoxy resin or silicone.
    [0024] The encapsulation layer may advantageously be deposited by chemical vapor deposition (CVD), which makes it possible to have an overlap of all the surfaces of the accessible stack. Thus, the encapsulation can thus be carried out directly on the stacks, the coating being able to penetrate all the available cavities.
    [0025] Advantageously, a second encapsulation layer may be deposited on the first encapsulation layer to increase the protection of the battery cells of their external environment. Typically, the deposition of this second layer can be achieved by a silicone impregnation. The choice of such a material comes from the fact that it withstands high temperatures and the battery can thus be easily assembled by soldering on electronic cards without appearance of glass transitions. Advantageously, encapsulation of the battery is performed on four of the six faces of the stack. The encapsulation layers surround the periphery of the stack, the rest of the protection to the atmosphere being provided by the layers obtained by the terminations. Preferably, the cathodic and anodic connections are offset laterally, which allows the encapsulation layer to function as a dielectric to avoid the presence of a short circuit on these ends.
    [0026] Once the stacking has been completed, and after the step of encapsulation of the stack if the latter is carried out, terminations (electrical contacts) are added at the level where the cathodic current collectors, respectively anodic, are apparent (uncoated). insulating electrolyte). These contact areas may be on opposite sides of the stack to collect current but also or on adjacent sides. To achieve the endings, the stack, possibly embedded, is cut according to section planes to obtain unitary battery components, with the bare on each of the cutting plane connections (+) and (-) of drums. The connections can then be metallized using plasma deposition techniques known to those skilled in the art and / or by immersion in a conductive epoxy resin (loaded with silver) and / or a molten tin bath. The terminations make it possible to resume the alternately positive and negative electrical connections on each of the ends. These terminations make it possible to make the electrical connections in parallel between the different battery elements. For this, only the connections (+) go out on one end, and the (-) are available on the other ends. This battery being entirely solid, and using a lithium-insertion material as anode material, the risks of formation of lithium metal dendrites during the charging steps are zero and the insertion capacity of the lithium anode becomes limited. . Also, in order to guarantee good cycling performance of the battery according to the invention, the battery architecture for which the surface capacitance of the cathodes is greater than or equal to the surface capacitance of the anodes is preferred.
    [0027] The layers of the battery being completely solid, the risk of lithium dendrite formation no longer exists when the anode is fully charged. Thus, such a battery architecture avoids the creation of battery cell overload. Also, the production of such a battery with surface capacities of cathodes greater than or equal to those of the anodes makes it possible to increase the performance in terms of service life, expressed in number of cycles. Indeed, the electrodes are dense and completely solid, the risk of loss of electrical contact between the particles is zero. 10
    权利要求:
    Claims (26)
    [0001]
    REVENDICATIONS1. A method of manufacturing a fully solid thin-film battery comprising the following steps: a) depositing a layer comprising at least one anode material (herein called "anode material layer") on its conductive substrate, preferably selected from the group consisting of a metal sheet, a metal strip, a metallized insulating sheet, a metallized insulating strip, a metallized insulating film, said conductive substrates, or their conductive elements, which can serve as anode current collector; b) depositing a layer comprising at least one cathode material (here called "layer of cathode materials") on its conductive substrate, preferably selected from the group formed by a metal sheet, a metal strip, a metallized insulating sheet, a metallized insulating strip, a metallized insulating film, said conductive substrates, or their conductive elements, being able to serve as a cathode current collector, it being understood that the steps a) and b) can be reversed; c) depositing on at least one layer obtained in step a) and / or b) a layer comprising at least one solid electrolyte material (here called "layer of electrolyte material") comprising a crosslinked solid polymer material having ionic groups; d) successively face-face stacking: - either a layer of anode material coated with a layer of solid electrolyte material obtained in step c) with a layer of cathode material coated or not with a layer solid electrolyte material obtained in step c); or a layer of cathode material coated with a layer of solid electrolyte material obtained in step c) with a layer of anode material coated or not with a layer of solid electrolyte material obtained at step c); e) thermal treatment and / or mechanical compression of the stack obtained in step d) is performed to obtain a fully solid thin-film battery.
    [0002]
    2. Method according to claim 1, characterized in that the crosslinked solid polymer material is selected from polymethyl methacrylates, polyamines, polyimides, or polysiloxanes.
    [0003]
    3. Method according to claim 1 or 2, characterized in that the ionic groups are chosen from the following cations: imidazolium, pyrazolium, tetrazolium, pyridinium, pyrrolidinium, such as n-propyl-n-methylpyrrolidinium ( also called PYR13) or n-butyl-n-methylpyrrolidinium (also called PYR14), ammonium, phosphonium or sulfonium; and / or among the following anions: bis (trifluoromethane) sulfonimide, bis (fluorosulfonyl) imide, or n- (nonafluorobutanesulfonyl) -n- (trifluoromethanesulfonyl) imide.
    [0004]
    4. Method according to any one of claims 1 to 3, characterized in that the crosslinked solid polymer material is obtained by a polymerization step of a mixture of monomers and / or oligomers and / or pre-polymers comprising one or more polymerizable groups thermally or photochemically, said mixture of monomers and / or oligomers and / or pre-polymers comprising one or more reactive groups for grafting said ionic groups, and then drying the crosslinked polymer material obtained.
    [0005]
    5. Method according to claim 4, characterized in that the thermal and / or photochemical polymerization is carried out directly on the layer (s) of anodes and / or cathodes.
    [0006]
    6. Method according to any one of claims 1 to 3, characterized in that the crosslinked polymeric material comprising ionic groups deposited in step c) is carried out among at least one of the following techniques: by soaking-withdrawal ( dip-coating), spin-coating, roll coating, doctor blade, electrospray, or electrophoresis.
    [0007]
    7. Method according to any one of claims 1 to 5, characterized in that the thickness of the electrolyte layer c) is less than 10 pm, preferably less than 5 pm, and even more preferably less than 2 pm .
    [0008]
    8. Method according to any one of claims 1 to 7, characterized in that the layers of anode, cathode and solid electrolytes are deposited among at least one of the following techniques: (i) physical deposition per phase steam (PVD), and more particularly by vacuum evaporation, by laser ablation, by ion beam, by cathodic sputtering, (ii) chemical vapor deposition (CVD), and more particularly plasma-assisted (PECVD) assisted by laser (LACVD), or assisted by aerosol (AA-CVD); (iii) electrospray; (iv) electrophoresis; (v) aerosol deposition; (vi) sol-gel; (vii) soaking, more particularly by dip-coating, spin-coating, or by the Langmuir-Blodgett process.
    [0009]
    9. Method according to any one of claims 1 to 8, characterized in that the anode, cathode and electrolyte layers are deposited by electrospray, electrophoresis, aerosol deposition, soaking, and are preferably all deposited by electrophoresis.
    [0010]
    10. Method according to any one of claims 1 to 9, characterized in that the layers of anode material and / or cathode further comprise electronically conductive materials, and in particular graphite, and / or conductive materials. lithium ions, of the type used to make the electrolyte films.
    [0011]
    11. Method according to any one of claims 1 to 10, characterized in that the anode layers and / or cathode are formed by a deposition of nanoparticles respectively of anode material, cathode of at least one electrospray, electrophoresis, aerosol deposition, soaking.
    [0012]
    12. The method of claim 11, characterized in that the layers of anode material, cathode and electrolyte are all deposited by electrophoresis.
    [0013]
    13. Process according to any one of Claims 1 to 12, characterized in that the heat treatment is carried out at a temperature of between 50 ° C and 300 ° C, preferably between 100 ° C and 200 ° C and / or the mechanical compression of the layers to be assembled is carried out at a pressure of between 10 and 100 MPa, preferably between 20 and 50 MPa.
    [0014]
    14. Process according to any one of claims 1 to 13, characterized in that the layer of anode material a) is made from material chosen from: (i) tin oxynitrides (of typical formula SnOxNy) ; (ii) lithium iron phosphate (of typical formula LiFePO4); (iii) mixed oxynitrides of silicon and tin (of typical formula SiaSnbOyNz with a> 0, b> 0, a-FLK2, 0 <y4, 0 <z3) (also known as SiTON), and in particular SiSno, 8701, 2N, 1.72; as well as oxynitrides in the form SiaSnbCcOyNz with a> 0, b> 0, a-FLK2, 0 <c <10, 0 <y <24, 0 <z <17; SiaSnbCcOyNzX, and SiaSnbOyNzXa with Xn at least one of F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb; (iv) the nitrides of the type SixNy (in particular with x = 3 and y = 4), SnxNy (in particular with x = 3 and y = 4), ZnxNy (in particular with x = 3 and y = 4), Li3_xMxN (with M = Co, Ni, Cu); (v) the oxides SnO2, Li4Ti5012, SnBo, 6P0, 402.9.
    [0015]
    15. Method according to any one of claims 1 to 14, characterized in that the layer of cathode material b) is made from cathode material chosen from: (i) the LiMn 2 O 4, LiCoO 2, LiNiO 2, LiMn 1 oxides, 5Ni, 504, LiMn1.5Ni0.5- xXx04 (where x is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earths, and where 0 <x <0.1), LiFeO2, LiMn1i3Ni1i3C01 / 304; (ii) LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2 (PO4) 3 phosphates; phosphates of formula LiMM'PO4, with M and M '(M # M') selected from Fe, Mn, Ni, Co, V; (iii) all the lithiated forms of the following chalcogenides: V205, V308, TiS2, titanium oxysulfides (TiOySz), tungsten oxysulfides (VVOySz), CuS, Cu52.
    [0016]
    16. Method according to any one of claims 1 to 15, characterized in that it further comprises a step f) of encapsulation of the battery obtained in step e) by depositing at least one layer of encapsulation of ceramic, vitreous or vitroceramic material.
    [0017]
    17. The method of claim 16, characterized in that it carries out anodic and cathodic terminations by metallization of the cut sections, preferably by deposition of a tin layer optionally deposited on a first layer of nickel and / or epoxy resin loaded with metal particles.
    [0018]
    18. Method according to any one of claims 1 to 17, characterized in that the conductive substrates are aluminum, copper or nickel, preferably nickel, and optionally coated with a noble metal selected from the following metals: gold, platinum, palladium, vanadium, cobalt, nickel, manganese, niobium, tantalum, chromium, molybdenum, titanium, palladium, zirconium, tungsten or any alloy comprising minus one of these metals.
    [0019]
    19. Battery obtainable by the method according to any one of claims 1 to 18.
    [0020]
    20. Battery according to claim 19, characterized in that the surface capacity of the cathode is greater than or equal to the surface capacitance of the anode.
    [0021]
    21. Battery according to claim 19 or 20, characterized in that the stack of cathode and anode layers is shifted laterally.
    [0022]
    22. Battery according to any one of claims 19 to 21, characterized in that it comprises at least one encapsulation layer, preferably a ceramic layer, glass or glass ceramic.
    [0023]
    23. Battery according to claim 22, characterized in that it comprises a second encapsulation layer deposited on said first encapsulation layer, said second encapsulation layer being preferably silicone.
    [0024]
    24. Battery according to claim 22 or 23, characterized in that said at least one encapsulation layer completely covers four of the six faces of said battery and partially the two remaining faces, located under the metallizations used for the connection of the battery.
    [0025]
    25. Battery according to any one of claims 19 to 24 characterized in that it comprises terminations at the level where cathodic current collectors, respectively anodic, are apparent.
    [0026]
    26. Battery according to claim 25, characterized in that the anode connections and the cathode connections are on the opposite sides of the stack.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2893623A1|2005-11-22|2007-05-25|Inst Nat Polytech Grenoble|Making crosslinked polymer film bearing ionic groups, useful as electrolyte for lithium battery, comprises extruding polymer material having prepolymer, polymerizing extruded polymer and grafting ionic groups|
    EP2432065A1|2010-09-20|2012-03-21|Commissariat à l'Énergie Atomique et aux Énergies Alternatives|Method for structuring a polymer layer and method for encapsulating a microbattery|
    FR2982083A1|2011-11-02|2013-05-03|Fabien Gaben|METHOD FOR PRODUCING SOLID ELECTROLYTE THIN FILMS FOR LITHIUM ION BATTERIES|
    WO2013064779A1|2011-11-02|2013-05-10|Fabien Gaben|Method for manufacturing all-solid-state thin-film batteries|
    GB8829118D0|1988-12-14|1989-01-25|Atomic Energy Authority Uk|Electrochemical cell manufacture|
    US5407593A|1993-11-15|1995-04-18|National Science Council|Polymeric electrolyte|
    DE69841867D1|1997-02-12|2010-10-07|Solicore Inc|Polymidbatterie|
    US6664006B1|1999-09-02|2003-12-16|Lithium Power Technologies, Inc.|All-solid-state electrochemical device and method of manufacturing|
    US6894143B2|2001-06-29|2005-05-17|Zeon Corporation|Polyether polymer, process for producing the same, composition for solid polymer electrolyte, and use thereof|
    JP4688406B2|2003-04-17|2011-05-25|セイコーインスツル株式会社|Electrochemical cell with terminal|
    WO2005085138A1|2004-03-06|2005-09-15|Werner Weppner|Chemically stable solid lithium ion conductors|
    US7776478B2|2005-07-15|2010-08-17|Cymbet Corporation|Thin-film batteries with polymer and LiPON electrolyte layers and method|
    WO2007086218A1|2006-01-24|2007-08-02|Murata Manufacturing Co., Ltd.|Chip battery|
    DE102007030604A1|2007-07-02|2009-01-08|Weppner, Werner, Prof. Dr.|Ion conductor with garnet structure|
    US20090202899A1|2008-02-11|2009-08-13|Pyszczek Michael F|Electrical apparatus with integral thin film solid state battery and methods of manufacture|
    US8986895B2|2009-02-04|2015-03-24|Kabushiki Kaisha Toyota Chuo Kenkyusho|Garnet-type lithium ion-conducting oxide and all-solid-state lithium ion secondary battery containing the same|
    JP2010186626A|2009-02-12|2010-08-26|Sumitomo Bakelite Co Ltd|Secondary cell|
    CN103518283A|2011-05-19|2014-01-15|丰田自动车株式会社|Solid-state lithium battery|
    JP6223725B2|2013-06-12|2017-11-01|新光電気工業株式会社|Battery and manufacturing method thereof|EP3436465A4|2016-04-01|2020-03-25|Nohms Tehcnologies, Inc.|Modified ionic liquids containing phosphorus|
    CN107331534A|2016-04-28|2017-11-07|北京纳米能源与系统研究所|A kind of fibrous ultracapacitor and its preparation method and application|
    US10707531B1|2016-09-27|2020-07-07|New Dominion Enterprises Inc.|All-inorganic solvents for electrolytes|
    EP3656010A4|2017-07-17|2021-08-11|Nohms Technologies, Inc.|Phosphorus containing electrolytes|
    KR101953738B1|2017-10-11|2019-03-04|한국에너지기술연구원|Composite Electrode with Ionic Liquid for All-Solid-State Battery, Method Of Manufacturing The Same, And All-Solid-State Lithium Battery Comprising The Same|
    WO2019200219A1|2018-04-12|2019-10-17|The Penn State Research Foundation|Porous metal-ion affinity material|
    FR3080862A1|2018-05-07|2019-11-08|I-Ten|METHOD FOR MANUFACTURING ANODES FOR LITHIUM ION BATTERIES|
    FR3080957B1|2018-05-07|2020-07-10|I-Ten|MESOPOROUS ELECTRODES FOR THIN FILM ELECTROCHEMICAL DEVICES|
    FR3080952B1|2018-05-07|2020-07-17|I-Ten|ELECTROLYTE FOR THIN FILM ELECTROCHEMICAL DEVICES|
    FR3080945A1|2018-05-07|2019-11-08|I-Ten|MESOPOROUS ELECTROLYTES FOR THIN-FILM ELECTROCHEMICAL DEVICES|
    CN109023484A|2018-06-29|2018-12-18|洛阳师范学院|A kind of preparation method of titanium disulfide film|
    FR3091036A1|2018-12-24|2020-06-26|I-Ten|METHOD FOR MANUFACTURING BATTERIES, AND BATTERY OBTAINED THEREBY|
    US11267707B2|2019-04-16|2022-03-08|Honeywell International Inc|Purification of bis imide|
    FR3097370A1|2019-06-13|2020-12-18|I-Ten|Lithium ion battery and its manufacturing process|
    WO2020257430A1|2019-06-19|2020-12-24|Arkema Inc.|Reticulated solid electrolyte separator|
    WO2021130697A1|2019-12-24|2021-07-01|I-Ten|Method for producing lithium-ion batteries, in particular high power lithium-ion batteries, and battery obtained by this method|
    FR3105593A1|2019-12-24|2021-06-25|I-Ten|METHOD OF MANUFACTURING LITHIUM ION BATTERIES, IN PARTICULAR HIGH POWER, AND BATTERY OBTAINED BY THIS PROCESS|
    EP3890077A1|2020-03-30|2021-10-06|I-Ten|Lithium-ion battery and manufacturing method thereof|
    WO2021225831A1|2020-05-04|2021-11-11|Soelect Inc.|Advanced solid electrolyte membranes and batteries made therefrom|
    FR3110774A1|2020-05-20|2021-11-26|I-Ten|Process for manufacturing a lithium ion battery|
    FR3111741A1|2020-06-23|2021-12-24|Hfg|HIGH ENERGY AND POWER DENSITY ANODE FOR BATTERIES|
    FR3111740A1|2020-06-23|2021-12-24|I-Ten|HIGH ENERGY AND POWER DENSITY ANODE FOR BATTERIES|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1456273A|FR3023418B1|2014-07-01|2014-07-01|COMPLETELY SOLID BATTERY COMPRISING AN ELECTROLYTE IN RETICULATED SOLID POLYMERIC MATERIAL|FR1456273A| FR3023418B1|2014-07-01|2014-07-01|COMPLETELY SOLID BATTERY COMPRISING AN ELECTROLYTE IN RETICULATED SOLID POLYMERIC MATERIAL|
    US15/323,727| US10804569B2|2014-07-01|2015-07-01|Solid-state battery including an electrolyte made of a cross-linked solid polymer material|
    KR1020177002878A| KR102324427B1|2014-07-01|2015-07-01|Solid-state battery including an electrolyte made of a cross-linked solid polymer material|
    JP2016575526A| JP6762237B2|2014-07-01|2015-07-01|All-solid-state battery containing an electrolyte made of a cross-linked solid polymer material|
    CN201580042827.1A| CN106797047B|2014-07-01|2015-07-01|Solid-state battery comprising electrolyte made of cross-linked solid-state polymeric material|
    EP15745536.1A| EP3164903B1|2014-07-01|2015-07-01|Solid-state battery including an electrolyte made of a cross-linked solid polymer material|
    PCT/FR2015/051814| WO2016001584A1|2014-07-01|2015-07-01|Solid-state battery including an electrolyte made of a cross-linked solid polymer material|
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