Battery, in particular thin film battery, comprising a novel encapsulation system

Abstract

To provide systems and methods for encapsulating thin film batteries and other electronic components that protect the components from the effects of air, moisture, and temperature.SOLUTION: A battery comprising an encapsulation system comprising a first coating layer deposited on the battery, a second coating layer deposited by atomic layer deposition on the first coating layer, and at least a third impermeable coating layer having a water vapor transmission rate (WVTR) of less than 10 - 5g / m2. d, made of a ceramic material and / or a low melting glass, deposited on the outer periphery of the battery or of the first coating layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to batteries, particularly thin film batteries, and more particularly to encapsulation systems for protecting the same. The invention relates more particularly to the field of lithium ion batteries that can be encapsulated in this way. The present invention provides a novel architecture and method for achieving particularly low self-discharge rates and long life. It further relates to a new method for manufacturing thin film batteries with encapsulation. [Background technology]

[0002] Some types of batteries, especially some thin-film batteries, are susceptible to oxygen and moisture, which can cause them to deteriorate. Since the battery is prone to malfunction, it must be sealed to ensure a long life. is extremely susceptible to moisture. The market demands a product lifespan of more than 10 years. Therefore, it is necessary to seal the battery so as to ensure this lifespan.

[0003] Thin-film lithium-ion batteries typically contain electrode and electrolyte layers that are about 1 μm to about 10 μm thick. This may include a stack of multiple unit cells. The location of the electrodes, especially at the edges of the electrodes in multi-layer batteries, is likely to be more susceptible to spontaneous discharge. The proximity and the quality of the disconnection lead to leakage current, i.e. creep that reduces battery performance. Short circuits due to this can be observed at the edges. This phenomenon is exacerbated when the electrolyte membrane is very thin. do.

[0004] This solid-state thin-film lithium-ion battery typically uses an anode with a lithium metal layer. The volume of the anode material is expected to change significantly during the charge and discharge cycles of the battery. More specifically, during the charge and discharge cycle, a portion of the lithium metal is converted to lithium. converted into ions, which are inserted into the structure of the cathode material, resulting in a decrease in the volume of the anode This cyclic change in volume can degrade the mechanical and electrical contact between the electrode and electrolyte layers. This reduces the battery's performance over its lifespan.

[0005] The cyclical change in the volume of the anode material also induces a cyclical change in the volume of the battery cell. This creates cyclic stresses on the containment system, which can affect the impermeability of the containment system. This makes the material more susceptible to cracks that cause loss of strength (or even integrity). This is yet another cause of deterioration in battery performance over its life.

[0006] More specifically, the active materials of lithium-ion batteries are highly resistant to the effects of air, and especially moisture. The migrating lithium ions react spontaneously with traces of water to form LiOH, All lithium ion conducting electrolytes and intercalation materials are It is insensitive to moisture. An example is Li4Ti5O 12 is the air or traces of water When it comes into contact with the metal, it does not deteriorate. 4+x Ti5O 12 Lithium in the form (x>0) As soon as the battery is filled with lithium, the excess lithium (x) inserted becomes sensitive to the atmosphere and It spontaneously reacts with a quantity of water to form LiOH. The reacted lithium then transfers electricity It is not available for storage, leading to a loss of battery capacity.

[0007] To prevent the active materials of lithium-ion batteries from being exposed to air and water, and to To prevent degradation, they must be protected by an encapsulation system. Inlet systems have been described in the literature.

[0008] Patent Document 1, among others, describes alumina (Al2O3), silica (SiO2), silicon nitride ( Si3N4), silicon carbide (SiC), tantalum oxide (Ta2O5), and amorphous carbon a stack of a first layer of a dielectric material selected from the group consisting of a first layer of a dielectric material, a second layer of a dielectric material, and a third layer of a dielectric material; An encapsulation system for a solid-state thin-film battery, comprising an impermeable sealing layer disposed over the two layers and covering the entire battery. The system is described.

[0009] Patent document 2 describes several systems for protecting thin-film lithium-ion batteries. The first system presented is a battery covered with an aluminum film deposited on the active components of the battery. However, this system includes a parylene layer to protect against the diffusion of air and water vapor. The system is only effective for about a month. The second system presented uses parylene (500 nm thick) The document states that the battery is degraded by atmospheric components. To slow down degradation, the battery is coated with an ultraviolet (UV) cured epoxy coating. It is stated that re-coating is preferable.

[0010] In addition, the applicant has disclosed in Patent Document 3 that the anode and cathode contact members In the first example, the first thin layer is A The first thin layer is deposited by laser diode (LD), and is in particular metallic. Furthermore, the first thin layer is a silver-filled epoxy resin. In the second example, two layers are provided. The first layer is a graphite filler material, while the second layer is a nano- Contains copper metal obtained from particle-filled ink.

[0011] In the prior art, most lithium-ion batteries are sealed around the battery cell and have a connector. Enclosed in a metallized polymer foil (called a "pouch") that is heat-sealed at the tab Because this package is relatively flexible, the negative and positive connections of the battery can be easily attached to the package around the battery. It is embedded in a heat-sealed polymer used to seal the package. However, the polymers used to heat seal the batteries are relatively permeable to atmospheric gases. Therefore, this weld between the polymer foils is completely impervious to atmospheric gases. No. Permeability increases with temperature, which appears to accelerate aging.

[0012] However, the surface area of ​​this weld exposed to the atmosphere is extremely small. The rest of the package is made of aluminum foil sandwiched between these polymer foils. Generally, two aluminum foils are combined to form a The effect of holes in the foil is minimized. Two defects in each strip This significantly reduces the possibility of misalignment.

[0013] This packaging technology allows for a 10x20cm package under normal use conditions. 2 The surface area of The 10Ah battery has a calendar life of approximately 10 to 15 years. If exposed to high temperatures, this lifespan can be reduced to less than 5 years, which is not sufficient for many applications. Similar techniques are used for other electronic components such as capacitors and active components. It is possible. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] US Patent Application Publication No. 2002 / 0071989 [Patent Document 2] U.S. Patent No. 5,561,004 [Patent Document 3] International Application Publication No. 2019 / 215410 Summary of the Invention [Problem to be solved by the invention]

[0015] Therefore, it is necessary to protect thin-film batteries and other electronic components from the effects of air, moisture, and temperature. There is a need for a system and method for encapsulating a component. The parts or batteries must be completely enclosed and airtight, and any To prevent short circuits due to creep, the edges of opposite polarities must be electrically isolated. It needs to be possible.

[0016] One object of the present invention is to at least partially overcome the above-mentioned drawbacks in the prior art. And so.

[0017] Another object of the present invention is to provide a lithium ion battery having an extremely long life and a low self-discharge rate. To do this. [Means for solving the problem]

[0018] The encapsulation system according to the invention is advantageously of the rigid type. The initial selection of the sealant is hard and dimensionally stable. The admission system is effective.

[0019] The present invention provides a method for producing an encapsulation system that can and is advantageously deposited in a vacuum. The battery of the present invention does not contain a polymer, but contains an ionic liquid. More specifically, it is of the solid or "quasi-solid" type. , in this case involving nano-confined ionic liquid-based electrolytes. From a chemical point of view, this nano-confined liquid electrolyte has good conductivity for the cations it conducts. To the extent that it provides mobility, it behaves like a liquid. From a structural point of view, this nano-restricted liquid The electrolyte is nano-confined even when processed in vacuum and / or at high temperatures, and the It cannot escape, so it does not act like a liquid.

[0020] Therefore, the battery according to the present invention containing the nano-confined ionic liquid-based electrolyte has To achieve this, vacuum and / or vacuum and high temperature treatments can be used. The edges of the layer are exposed by cutting, and after impregnation, these edges are used to make electrical contacts. The method of the present invention also effectively covers the mesopore surfaces. Suitable.

[0021] The method of the present invention is also well suited to covering the mesopore surfaces.

[0022] The above-mentioned object can be achieved by at least one of the objects of the present invention as described below. At least one is achieved.

[0023] The present invention provides a battery as a first object, the battery comprising: - Anode current collecting substrate, anode layer, layer of electrolyte material or electrolyte-impregnated separator At least one unit cell, which includes, in sequence, a cathode layer, a cathode layer, and a cathode current collecting substrate. and when the battery includes a plurality of unit cells, the second one is the layer order shown. and at least one unit cell, the first one being positioned on top of the second one, and so on. - Outside the above-mentioned unit cell, or all the above-mentioned unit cells if more than one exists covering at least a portion of the periphery; - Optionally, preferably Parylene, Parylene F, polyimide, epoxy resin, silicone a polyamide, a sol-gel silica, an organosilica, and / or a mixture thereof; a first coating layer deposited on the battery; - optionally made of an electrically insulating material, deposited on the cell or the first coating layer by atomic layer deposition; a second coating layer; and - At least one element used to make electrical contact between the unit cell and an external conductive element an anode contact member; - at least one cathode core used to make electrical contact with an external conductive element; and a contact member, the battery includes a first contact surface defining at least one anode connection zone; the cell includes a second contact surface defining at least one cathode connection zone; The encapsulation system comprises: - 10 -5 g / m 2 Ceramic materials with a water vapor transmission rate (WVTR) of less than .d and / or made from low-melting glass, preferably glass having a melting point below 600°C. and further comprising at least a third impermeable coating layer disposed on the outer periphery of the battery or the first coating layer. , When the second coating layer is present, the series of the second coating layer and the third coating layer is , which can be repeated z times, where z≧1, and at least a third coating layer is deposited on the outer periphery; The final layer of the encapsulation system is made of ceramic material and / or low melting point glass. -5 g / m 2 an impervious covering layer as described above having a water vapor transmission rate (WVTR) of less than .d. .

[0024] The battery of the present invention can be adopted individually or according to any technically suitable characteristics. In other features, - Preferably 10 -5 g / m 2 3rd class non-woven fabric with a water vapor transmission rate (WVTR) of less than .d The permeable coating layer has a thickness of 1 μm to 50 μm, more preferably 1 μm to 10 μm, and even more preferably The thickness is usually between 1 μm and 5 μm, - each of the anode contact member and the cathode contact member; - located in at least the anode connection zone and at least the cathode connection zone, Materials filled with electrically conductive particles, preferably polymeric resins and and / or sol-gel derived materials, more preferably graphite-filled polymers. a first electrical connection layer including a polymer resin; - a second electrical connection layer comprising a metal foil disposed on the first layer of material filled with electrically conductive particles; Including, the metal foil is of the self-supporting type and is advantageously applied to the above-mentioned first electrical connection layer, - the metal foil is produced by rolling or electroplating, - the thickness of the metal foil is comprised between 5 and 200 micrometers, and this metal foil is particularly , nickel, stainless steel, copper, molybdenum, tungsten, vanadium, tantalum, titanium made from one of the following materials: tungsten, aluminum, chromium, and alloys containing these; - each of the anode contact member and the cathode contact member has a second electrical connection; a third layer including a conductive ink disposed on the layer; - This battery is - at least partially made of a conductive material and disposed near an end face of the unit cell; Electrical connection support, - two separate areas of the connection support, each forming an electrical connection path, are spaced apart from each other; Electrical insulating means, which can be insulated to The first side of each unit cell can be electrically connected to the first electrical connection path. electrically connecting the node contact member and the second side of each unit cell to a second electrical connection path; the cathode contact member as described above, the electrical connection support is of the single-layer type, in particular a metal grid or a silicon intermediate layer, The electrical connection support comprises several layers arranged one above the other, in particular a printed circuit board. It is of the type - an impervious coating layer is provided, in particular on the respective anode contact elements and cathode contact elements; a primary impermeable coating layer that does not cover the contact element, and in particular a layer that covers all or part of the contact element and in particular includes a further impermeable covering layer at least partially covering the electrical connection support. , - The battery is a lithium-ion battery, - This is a solid-state lithium-ion battery, - it is designed and configured to have a capacity of 1 mAh or less, - It is designed and configured to have a capacity of more than 1 mAh.

[0025] The present invention also relates to a method for manufacturing the above-mentioned battery, the method comprising: (a) coated with an anode layer and optionally impregnated with a layer of electrolyte material or electrolyte; At least one anode foil, hereinafter referred to as the anode foil, is coated with a layer of a separator providing an anode current collecting substrate foil; (b) coated with a cathode layer and optionally impregnated with a layer of electrolyte material or electrolyte; At least one cathode foil is coated with a layer of a separator, hereinafter referred to as the cathode foil. providing a cathode current collecting substrate foil; (c) at least one anode current collecting substrate, at least one anode layer, and an electrolyte material; At least one layer of separator impregnated with a material or electrolyte, at least one cathode At least one electrode is then formed to obtain a cathode layer, and at least one cathode current collecting substrate. Step of preparing a stack (I) of alternating node foils and at least one cathode foil. P, (d) mixing the alternating layers obtained in step (c) to form a unified stack; heat treating and / or mechanically compressing the foil stack; (e) - optionally, preferably parylene, parylene F, polyimide, epoxy resin, silicones, polyamides, sol-gel silica, organosilica, and / or mixtures thereof At least one first coating layer in the battery is selected; - optionally made of an electrically insulating material and deposited by atomic layer deposition on the battery or on the first coating layer; a second coating layer, and - Preferably 10 -5 g / m 2 It has a water vapor transmission rate (WVTR) of less than .d and is ceramic. from a glass material and / or a low melting point glass, preferably a glass having a melting point below 600°C. and depositing at least a third impermeable coating layer on the outer periphery of the battery or the first coating layer. encapsulating the integrated stack by stacking the This sequence of at least one second coating layer and at least one third coating layer is z The process can be repeated several times, and z≧1 is formed by depositing at least a third coating layer on the outer periphery of the coating. The final layer of the system is made of ceramic material and / or low melting point glass. -5 g / m 2.d or less of the impermeable covering layer (WVTR) Tep, (f) Cutting the substrate to expose at least the anode and cathode connection zones. making two cutouts (Dn, D'n) to form a stack; (g) fabricating an anode contact member and a cathode contact member. nothing.

[0026] The processes of the present invention can be adopted individually or according to any technically suitable features. In other features of the - the anode contact member and the cathode contact member are fabricated by - made from a material filled with electrically conductive particles, preferably filled with electrically conductive particles The first electrode is made of a polymer resin and / or a material obtained by a sol-gel method. Preferably, the connection layer is provided at least in the anode connection zone and at least in the cathode connection zone. At least the contact surface and at least the cathode contact zone depositing at least a contact surface including the contact zone; Optionally, said first layer is made of a polymeric resin and / or a silica gel filled with electrically conductive particles. When made from materials obtained by the gel method, a drying step is followed by the above-mentioned high molecular weight polymer. polymerizing the polymer resin and / or the sol-gel material; a second electrical contact disposed on the first electrical connection layer, preferably a metal foil or a metal ink; A connecting layer is deposited on the first layer, and in the latter case the drying step described above is also performed on the second electrical connecting layer described above.

[0023] The method may be performed after deposition of a subsequent layer, - a metal foil is formed by rolling, and then the metal foil thus formed is subjected to a first Add to the electrical connection layer, - the metal foil is either ex situ or in situ with respect to the first metal connection layer; It is directly formed by electroplating at - the method as described above, after step (g), comprises coating with a first electrical connection layer and a second electrical connection layer; In at least the anode and cathode connection zones of the battery, (h) depositing a conductive ink; - Low melting point glass is SiO2-B2O3, Bi2O3-B2O3, ZnO-Bi2O 3-B2O3, TeO2-V2O5, and PbO-SiO2; - the second coating layer is deposited at low temperature by PECVD, preferably by HDPCVD or is deposited by ICP CVD, - the second coating layer is an oxide and / or nitride and / or Ta2O5 and / or oxynitride and / or Si x N y and / or SiO2 and / or SiON and / or amorphous silicon and and / or SiC, - the impermeable sealing means is provided after the electrical connection support is disposed adjacent the first end face of the unit stack. Coated, - at least a portion of the impermeable sealing means is adapted to seal the electrical connection support member near the first end face of the unit stack; coated before being placed next to each other, - At least the primary impervious coating layer shall have electrical connection supports adjacent the first end face of the unit stack. before placement, and then a further impervious covering layer is applied to the electrical connection support the part is disposed near the first end face and then coated, - - providing a frame (105) used to form a plurality of supports (5); thing, - a first end of a stack of multiple units arranged in multiple lines and / or multiple rows; placing the frame described above near the surface; - longitudinally and / or longitudinally stacking these to form a plurality of electrochemical devices; or making at least one cutout, in particular a plurality of cutouts, in the transverse direction, provide.

[0027] Finally, the present invention provides a device capable of supplying electrical energy to a main body and an electrical energy consuming device. and the battery, wherein the electrical connection support of the battery is fixed to the body. The object is an electrical energy consuming device.

[0028] It is necessary to find that the applicant has identified certain shortcomings in the prior art with respect to impermeability. In particular, the applicant has developed a sealing system and a contact member. It was noted that the boundary between the electrodes forms a critical zone. However, it is a preferred gateway for various components, especially water molecules, which can interfere with the operation of the In the prior art, the aforementioned boundaries do not provide a sufficient barrier to the aforementioned components. However, the impermeability is not satisfactory.

[0029] On the other hand, in the present invention, the presence of an impermeable coating layer overcomes the drawbacks of the prior art. More specifically, this coating layer provides a particularly effective barrier against the harmful components mentioned above. Furthermore, this coating layer is advantageously relatively thick. Thus, for example, in ALD This prevents the mechanical damage that occurs in the deposited material. The invention is based on a rigid material that prevents water vapor from passing through the interface between the encapsulation system and the contact members. A non-permeable enclosure is obtained.

[0030] Particularly advantageously, the battery according to the invention comprises a metal foil in its second electrical connection layer. As will be understood within the scope, such metal foils advantageously have a "free-standing" structure. This is fabricated ex situ and then brought into contact with the first layer of the above metal foil. is obtained, for example, by rolling, in which case the rolled foil contains either partially or completely A final softening anneal can be performed.

[0031] The metal foils used in the present invention may also be deposited by other methods, particularly electrochemical deposition or electroplating. In such cases, this is typically achieved by, as described herein above. Alternatively, this can be done in situ, i.e. That is, it can be directly applied to the first layer described above.

[0032] In any event, the metal foil, once fabricated, has a controlled thickness.

[0033] Copper metal obtained from nanoparticle-filled inks as described in U.S. Patent No. 5,949,623, cited herein above. It should be noted that the layer containing is not at all a metal foil as understood within the scope of the present invention. More specifically, the layers disclosed in this prior art document are None of the conditions are met.

[0034] Typically, the thickness of this metal foil is comprised between 5 and 200 micrometers. In addition, the metal foil is advantageously sufficiently dense and electrically conductive. Metal foils include nickel, stainless steel, copper, molybdenum, tungsten, vanadium, and titanium. It can be made from materials such as titanium, aluminum, chromium, and alloys containing these. This can be done.

[0035] The use of such a metal foil in combination with a coating layer provides advantages over the techniques described above, particularly with regard to impermeability. In this regard, such metal foils are characterized by the enhanced chemi- cal effect obtained by the deposition of metal nanoparticles. It should be noted that the impermeability of the concrete is much higher than that of the concrete. Ultimately, sintering results in a film that contains more point defects and is less hermetic.

[0036] Furthermore, the surfaces of metal nanoparticles are often covered with a thin oxide film, the properties of which affect their electrical conductivity. On the other hand, the use of metal foil improves airtightness and electrical conductivity. To make.

[0037] Furthermore, the use of metal foil allows a wider range of materials to be used. It ensures that the chemical compositions in contact with the anode and cathode, respectively, are electrochemically stable. On the other hand, the prior art provides a relatively limited selection of materials available for forming nanoparticles.

[0038] The drying step as claimed in the appended claims is in particular carried out by drying the metal foil in a manner such that the metal foil is at least Preferably, at least an anodized aluminum is added to the cathode connection zone and / or at least to the cathode connection zone. At least the contact surface including the cathode connection zone and / or at least the cathode connection zone Ensure that the adhesive adheres to at least the contact surface.

[0039] The accompanying drawings illustrate diagrammatically encapsulated multilayer batteries according to various embodiments of the present invention. These correspond to cross sections perpendicular to the thickness of the layer. [Brief explanation of the drawings]

[0040] [Figure 1] FIG. 1 shows a battery comprising a single unit cell, the encapsulation system comprising three separate layers. [Figure 2] FIG. 2 shows a battery comprising a stack of four unit cells, the encapsulation system comprising three separate layers. [Figure 3] FIG. 3 shows a battery comprising a stack of four unit cells, the encapsulation system comprising three series of two separate layers. [Figure 4A-B] In Figure 4, Figures 4A and 4B are perspective views showing stacks of alternating anode and cathode foils included in two alternative embodiments of methods for manufacturing batteries according to the present invention. [Figure 5] FIG. 5 is a longitudinal cross-sectional view of the cell of FIG. 1 further including a conductive support. [Figure 6] FIG. 6 is a longitudinal cross-sectional view of an alternative embodiment to that shown in FIG. [Figure 7] FIG. 7 is a perspective view showing a frame that allows multiple cells in FIG. 5 or FIG. 6 to be fabricated together. [Figure 8] 8 is a front view similar to that of FIG. 5 illustrating steps in making the battery shown in FIG. [Figure 9] FIG. 9 is an overhead view showing cutouts made in the frame of FIG. 7 to provide access to multiple cells. [Figure 10] FIG. 10 is a front view illustrating the incorporation of the battery of FIG. 5 into an energy consuming device. [Figure 11] FIG. 11 is a front view similar to that of FIG. 10, showing an alternative embodiment to that shown in FIG. 10, particularly with regard to the structure of the conductive support portion. [Figure 12] FIG. 12 is an exploded perspective view of the various components of the conductive support of FIG. DETAILED DESCRIPTION OF THE INVENTION

[0041] The present invention relates to a so-called electrochemical unit cell, i.e., an anode current collector, an anode layer, an electrolyte A layer of material or a layer of electrolyte-impregnated separator, a cathode layer, and a cathode current collector The current collectors described above are also referred to as "current collecting substrates", i.e., anodes. They are also called current collecting substrates and cathode current collecting substrates.

[0042] The present invention further applies to batteries comprising a stack of multiple unit cells.

[0043] The encapsulation, which represents one major feature of the present invention, is described herein.

[0044] After the fabrication of the stack of layers that make up the battery and its mechanical processing for the consolidation of the stack and / or after a heat treatment step (which treatment involves the application of both high pressure and high temperature) This stack is enclosed in an encapsulation system to protect the battery cells from the atmosphere. The encapsulation system is formed by depositing a barrier layer. Therefore, it must be chemically stable, able to withstand high temperatures, and impermeable to the atmosphere.

[0045] The stack is - Optionally, preferably Parylene, Parylene F, polyimide, epoxy resin, acrylate acrylates, fluoropolymers, silicones, polyamides, sol-gel silica, organosilica, and and / or a mixture thereof, deposited on the stack of anode and cathode foils. , a dense insulating first coating layer, and - optionally made of an electrically insulating material, and connected to the stack of anode and cathode foils or to the above-mentioned a second coating layer deposited on the first coating layer by atomic layer deposition; and - In essential features, preferably 10 -5 g / m 2 Water vapor transmission rate (WV) of less than .d TR), ceramic materials and / or low-melting glasses, preferably with a melting point below 600°C The stack of anode and cathode foils or the first coating layer is made of glass having a point. It can be covered with an encapsulation system including at least a third impervious coating layer deposited around the perimeter. , This sequence of at least one second coating layer and at least one third coating layer is z The method can be repeated several times, and z≧1, and the method can be performed by depositing the third coating layer on the outer periphery of the coating layer. The final layer of the encapsulation system is made of a ceramic material and / or a low-melting glass. , preferably 10 -5 g / m 2 Impervious covering with a water vapor transmission rate (WVTR) of less than .d It is a covering layer.

[0046] This sequence can be repeated z times, z ≥ 1. This means that as the value of z increases, It has a barrier effect that increases with increasing temperature.

[0047] Water vapor transmission rate is the subject of U.S. Pat. No. 7,624,621 and is also Published in Hin Solid Films 6+550 (2014) 85-89 In the article "Structural properties" by A. Mortier et al. of ultraviolet cured polysilazane gas b Also described in "Arrier Layers on Polymer Substrates" It can be measured using methods known in the art.

[0048] Typically, the optional first coating layer is a silicone (e.g., by impregnation or hexafluoroethylene). Deposited by plasma-assisted chemical vapor deposition from methyldisiloxane (HMDSO), epoxy Polyxylylene, polyimide, polyamide, polyparaxylylene (also known as poly(p-xylylene) The group consisting of: The first coating layer, when deposited, protects the battery's sensitive components from their environment. The thickness of the above-mentioned first coating layer is preferably between 0.5 μm and 3 μm.

[0049] This first coating layer is particularly useful when the electrolyte and electrode layers of the battery are porous, This first layer acts as a planarizing layer that also has a rear effect. As shown, the layer can be lined with an open microporous surface at its surface.

[0050] In this first coating layer, various parylene variants can be used. , Parylene D, Parylene N (CAS1633-22-3), Parylene F, or Parylene C A mixture of D, N, and / or F can be used. Parylene has high thermodynamic Dielectric, transparent, with thermal stability, excellent resistance to solvents, and extremely low permeability Parylene F is a semi-crystalline material. Parylene also has barrier properties. It is preferable within the range.

[0051] This first coating layer is advantageously applied to the cell stack surface by chemical vapor deposition (CVD). This is obtained by condensing the deposited gaseous monomers, which are available in the stack. This results in a conformal, thin, uniform coating on all available surfaces. The covering layer is advantageously hard and is not considered to be a flexible surface.

[0052] The second coating layer, which is also optional, is formed of an electrically insulating material, preferably an inorganic material. This means that all available surfaces of the stack that have been covered with the first coating layer are covered. Atomic layer deposition (ALD), PECVD, HDPCVD to obtain conformal coatings (High Density Plasma Chemical Vapor Deposition), or ICP CVD (Inductively Coupled Plasma Chemical Vapor Deposition Layers deposited by ALD are mechanically very fragile and Requires a hard support surface to provide protection. Deposits a weak layer on a flexible surface. This can lead to the formation of cracks and loss of integrity of this protective layer. The growth of the deposited layer is influenced by the properties of the substrate. Layers deposited by ALD on substrates with this protective layer will grow inhomogeneously, and the completeness of this protective layer will be compromised. For this reason, this optional second layer, if present, is preferably It abuts any first layer, thereby ensuring a chemically homogeneously grown substrate.

[0053] ALD deposition techniques can cover extremely rough surfaces to be completely impervious and conformal. This is particularly well suited to forming a layer that is free of defects such as holes ("pinhole-free" layers). This allows the creation of a conformal layer, which represents a very good barrier. WVTR is extremely low. WVTR (Water Vapor Transmission Rate) is a measure of the water vapor permeability of an encapsulation system. The lower the WVTR, the more impermeable the encapsulation system. The thickness of this second layer is advantageously a function of the desired level of impermeability to gases, i.e. Selected as desired WVTR, especially ALD, PECVD, HDPCVD, and ICP The choice depends on the deposition technique used, which can be from CVD.

[0054] The second coating layer may be, for example, an oxide, Al2O3 or Ta2O5 type, nitride, phosphazene, or the like. Ceramic or glassy materials in the form of sulphates, oxynitrides or siloxanes, or This second coating layer can be made of a glass ceramic material. It has a thickness between 10 nm and 10 μm, preferably between 10 nm and 50 nm.

[0055] The first coating layer is deposited by ALD, PECVD, HDPCVD (High Density Plasma Chemical Vapor Deposition), or This second coating layer is deposited by ICP CVD (Inductively Coupled Plasma Chemical Vapor Deposition) First, it makes the structure impervious, i.e., it makes it possible to prevent water from moving into the object. Then, to prevent its deterioration, a first coating layer, preferably made of Parylene F, is applied in the atmosphere. This allows protection from the elements, especially from air and moisture, and from heat exposure. The second coating layer improves the life of the encapsulated battery.

[0056] The second coating layer may also be applied directly to the anode and cathode foil stack, i.e., on top of the anode and cathode foil stack. If the first coating layer described above has not been deposited, it can be deposited.

[0057] The third coating layer must be impermeable, preferably 10 -5 g / m 2 .dnot This means that the third coating layer has a water vapor transmission rate (WVTR) of 100%. and a ceramic material and / or a ceramic material deposited on the outer periphery of the cathode foil stack or the first coating layer. Alternatively, the glass may be formed from a low-melting glass, preferably a glass having a melting point lower than 600°C. The ceramic and / or glass material used for this third layer is advantageously: - Low melting point glass (typically below 600°C), preferably SiO2-B2O3, Bi2 O3-B2O3, ZnO-Bi2O3-B2O3, TeO2-V2O5, and PbO-S iO2, - Oxides, nitrides, oxynitrides, Si x N y , SiO2, SiON, amorphous silicon The material is selected from the group consisting of silicon carbide (SiC), ... and silicon carbide (

[0058] These glasses can be deposited by molding or dip coating.

[0059] The ceramic material is advantageously prepared at low temperature by PECVD or preferably by HDPC It is deposited by VD or ICP CVD and has good impermeability by these methods. A layer can be deposited.

[0060] The stack thus coated then has an anode connection zone and a cathode connection zone. Any suitable cutting is performed along the cutting lines D'n and Dn to expose the connection zone and obtain the unit cells. be severed by forceful means.

[0061] The cathode connection zone and the corresponding anode connection zone are connected to the contacts. Add contact elements (electrical contacts). These contact zones are preferably: Contacts are placed on opposite sides of the stack of cells to collect current (side current collectors). The material is preferably present in at least the cathode connection zone and at least the anode connection zone. , the surface of the coated and cut stack including at least the cathode connection zone, and The coated and cut stack faces containing at least the anode connection zone. do.

[0062] Preferably, the contact members are made of a material filled with electrically conductive particles, preferably an electrically conductive Polymer resins and / or sol-gel derived materials filled with conductive particles, more preferably a first electrical connection layer, the first layer comprising a polymeric resin filled with graphite; and a second layer of metal foil, which is subsequently connected to the cathode connection zone and It is configured adjacent to the anode connection zone.

[0063] The first electrical connection layer is adapted to electrically connect the electrical circuit when the electrical circuit is subjected to thermal and / or vibration stresses. The subsequent second electrical connection layer can be applied without interrupting the electrical connection, providing "flexibility" to the connection. It can be fixed.

[0064] The second electrical connection layer is advantageously a metal foil. This second electrical connection layer has a permanent resistance to moisture. Generally, for a given thickness of material, metals are used to provide substantial protection to the battery. , which are generally less impermeable to the passage of water molecules than ceramic-based membranes. This allows for the creation of extremely impermeable membranes, even more impermeable than polymer-based membranes. This is because the WVTR at the contacts is lowered, which helps to improve the calendaring of the battery. It extends the lifespan.

[0065] Typically, each first layer is attached to an anode termination or a cathode termination, respectively, by adhesive bonding. In consideration of this, a conductive adhesive layer can be used. Two conductive adhesive layers may be used, each of which has a different It is "continuous" i.e. the first layer covers the termination while the second layer covers the first layer. Advantageously, these two conductive adhesives have different physicochemical properties, in particular different wetting properties. can have:

[0066] Typically, the metal foils described herein above are connected to the electrodes by adhesive bonding, more precisely It is fixed to the first layer by a conductive adhesive that must be electrochemically stable when in contact with the This metal foil, bonded using a conductive adhesive, improves the impermeability of the termination and Lowers electrical resistance. This technical effect is noticeable regardless of the method used to manufacture the foil. is.

[0067] Advantageously, a third electrical connection layer comprising a conductive ink can be deposited on the second electrical connection layer. The purpose is to reduce WVTR and extend battery life.

[0068] The contact members allow for alternating positive and negative electrical connections at each end. These contact members can provide parallel electrical connections between different battery elements. For this purpose, only the cathode connection protrudes at one end and the anode connection at the other. Available at the end.

[0069] 1-3 are described herein to illustrate the present invention and various embodiments of the present invention. 1 shows a schematic representation of a multilayer cell encapsulated in a PET film, which corresponds to a cross section perpendicular to the thickness of the layers.

[0070] Using the Cartesian coordinate system XYZ, - Axis XX is the first horizontal axis, i.e., contained in the plane of the various layers that make up the stack Furthermore, this axis XX is called the transverse axis, i.e. it extends transversely to the foil. In particular, it is perpendicular to the plane of the contact members described herein below. - Axis YY is the second horizontal axis, which is also contained in the plane of the layers of the stack. This axis YY is sagittal This is called the axis, i.e. it runs from the back to the front of the foil. It is parallel to the surface. - Finally, axis ZZ is perpendicular to each of the above axes and extends up and down. This is also called the front axis.

[0071] FIG. 1 shows a battery I according to a first embodiment of the present invention. This battery comprises a single unit cell 1 More specifically, the unit cell 1 includes an anode layer 2, an electrolyte layer 3, and a cathode layer 2. The encapsulation system 4 is formed by a first layer 11 as described herein above, Then a second coating layer 12 as described herein above, and finally a second coating layer 13 as described herein above. The third coating layer 13 comprises three different layers arranged one on top of the other.

[0072] Here, the encapsulation system covers four of the six sides of the cell (which corresponds to a parallelepiped). (if applicable). Preferably laterally opposite each other, not covered by a containment system. Each of the two opposite sides defines at least one electrical connection zone, and any short circuit To prevent scratches, the first side not covered by the encapsulation system is the anode connection zone. The second surface not covered by the encapsulation system defines a cathode connection zone.

[0073] The battery further includes contact members generally designated by the reference numerals 8 and 8'. As described herein above, each contact element comprises a first electrical connection layer 5 or 5' and It includes a second electrical connection layer 6 or 6'.

[0074] FIG. 2 shows a battery II according to a second embodiment of the present invention. This battery II is made up of four units. The encapsulation system 4 comprises a stack of cells 1a, 1b, 1c, 1d. The contact members 8, 8' comprise three different layers as described above with respect to FIG. The same as described above.

[0075] 3 shows a battery III according to a third embodiment of the present invention. This battery is similar to that shown in FIG. The encapsulation system 4 comprises a stack of four unit cells as described. different layers, namely the second coating layer 12 as described herein above and the Finally, the contact members 8, 8' are as described in relation to FIG. Similar to that described above in the specification.

[0076] The cells I, II, and III in Figures 1 to 3 are impermeable, which is the main criterion of the present invention. It should be noted that the conditions for the contact element 8 must be met. , 8' are made of conductive materials that meet this impermeability standard. For example, metal powders (e.g., chromium, aluminum, copper, and of the type filled with particles (and preferably nanoparticles) of other metals that are electrochemically stable at It is a conductive glass.

[0077] Advantageously, as known per se, a plurality of units such as those described hereinabove The stack can be fabricated together. This is the overall method for manufacturing the battery in the present invention. In particular, the use of a series of alternating cathode layers and corresponding anode layers or foils Stacks thus formed can be made with large dimensions.

[0078] For example, the type known from French patent application FR 3091036 filed by the applicant The physical and chemical structure of each anode foil or cathode foil is not within the scope of the present invention. Each anode foil or corresponding cathode foil is an anode active material. Each of these active layers may be solid. In addition, the thickness of two adjacent foils can be To prevent electrical contact between the electrodes, a layer of electrolyte or a layer of separator impregnated with a liquid electrolyte is placed. At least one of these two foils is placed in contact with the foil on the opposite side. The electrolyte layer or separator impregnated with liquid electrolyte, which is not shown in the figures, is opposite. It is sandwiched between two foils of a polarity, i.e., an anode foil and a cathode foil.

[0079] These layers define so-called free zones that allow separation between different end cells. Within the scope of the present invention, various shapes may be applied to this empty zone. It is possible to use the method already proposed by the applicant in French patent application no. 3091036. As shown, this void zone can be H-shaped. 11 shows a stack 1100 between a node foil or layer 1101 and a cathode foil or layer 1102. As shown in this figure, the above-mentioned H-shaped anode vacant zone 1103 and the corresponding Cuts are made in these various foils to form the sword-free zones 1104.

[0080] Alternatively, these open zones may be I-shaped. 12 shows a stack 1200 between a cathode foil or layer 1201 and a cathode foil or layer 1202. As shown in FIG. 4B, the above-mentioned I-shaped anode vacant zone 1203 and the corresponding cathode Cutouts are made in these various foils to form open zones 1204 .

[0081] Preferably, once the fabrication of the separate unit stacks is complete, each anode and each The cathode is separated from each secondary electrode by a space that is free of any electrode material, electrolyte, and / or conductive substrate. In yet another embodiment, not shown, the air The zone should be U-shaped, or should be different from H-shaped or I-shaped. In any case, the H-shape or I-shape is preferable. During the process, it can be filled with resin.

[0082] FIG. 5 and the following figures show a further advantageous alternative embodiment in which the battery described above further includes a support. These figures show the stack 1, the front encapsulation areas 40, 41 and the contacts The members 8, 8' are shown diagrammatically. The support 50 described above is substantially planar and typically has a width of 300 mm. The support has a thickness of less than 100 μm, preferably less than 100 μm. Coating with a thin layer of nickel and tin to improve its welding properties An electrically conductive material, typically a metallic material, especially aluminum, copper, or stainless steel, can be used. The so-called front faces of the supports are respectively given the reference number 51 and the stack 9 and the opposite rear surface is given the reference numeral 52.

[0083] This support is perforated, i.e., a central base plate 55 and two opposite sides The support has gaps 53, 54 that define side strips 56, 57. The separate regions 55, 56, and 57 are electrically isolated from one another. As shown, the side strips 56, 57 are electrically insulated from each other and from the battery. In the illustrated example, the electrical insulation is This is achieved by providing open voids 53, 54 filled with hardening material as seen below. Alternatively, these voids may be filled with a non-conductive material, such as a polymer, ceramic, or glass. The lath can be filled.

[0084] In the example shown, the support and the stack are connected to each other by layer 60. are typically formed by a non-conductive adhesive, especially of the epoxy or acrylate type. Alternatively, the support and the stack may be firmly fixed to each other by welding (not shown). The thickness of this layer 60 is typically comprised between 5 μm and 100 μm, in particular about 50 In the major plane of the support 50, this layer has a thickness equal to 1 μm, as described in detail herein below. so as to insulate the anode contact member and the cathode contact member from each other. At least partially covering the aforementioned gaps 53, 54. Furthermore, a pad 30 of conductive adhesive, 31 can fix the contact member to the support part 5 while ensuring electrical continuity. .

[0085] In a first aspect corresponding to the embodiment shown in FIG. 5, the contact members 8, 8' are formed. The material used must be capable of fulfilling the impermeable sealing function according to the above criteria. This material is typically one of the materials listed hereinabove with respect to the description of the first three figures. In such cases, no further encapsulation is necessary. More specifically, The presence of the permeable contact members and encapsulation allows the anode and cathode unit stacks to be Protect the equipment against the ingress of potentially harmful gases.

[0086] In a second aspect, corresponding to the embodiment shown in FIG. 6, the contact members 8, 8' are formed. The material used is not impermeable as understood within the scope of the present invention. Advantageously, it comprises a further so-called encapsulation layer 45, shown in solid lines in FIG. The stack is "resealed" to give it the desired impermeability. The material of this layer 45 is defined as the last layer of the encapsulation system. The layer 45 is advantageously made from a ceramic material and / or a low-melting glass, while 0 -5 g / m 2 In this embodiment, the water vapor transmission rate (WVTR) is less than 0.05. Thus, the "impermeable coating" layer is the first encapsulation system, which forms the so-called primary impermeable coating layer. The final layer of the barrier is formed by a further layer 45, which forms the so-called further impermeable covering layer. will be done.

[0087] To ensure the main criteria of impermeability, this further encapsulation layer 45 is first This covers the contact members 8, 8'. Furthermore, this is the first encapsulation layer 41 and the support portion 50. Finally, it also extends into the intermediate space between the support and the facing surface. 3, 54. At the bottom of FIG. 6, reference numeral 45 is shown in three of these specific zones. Therefore, no components harmful to the proper functioning of the battery are present in the anode and cathode. In other words, the present invention eliminates this harmful It blocks any possible "gateways" to the compound.

[0088] In a third embodiment (not shown), only the unit stack is first formed with a conductive adhesive layer sandwiched therebetween. The stack is then placed on a support. The sides of the stack are then covered with contact members. The unit stack already provided with these contact members without an encapsulation system also has its support. Finally, the encapsulation system can be placed in the overall The soil will be deposited while taking care to ensure impermeability.

[0089] Finally, in one advantageous embodiment of the invention, the battery further comprises a curing system. This can be done by first attaching the battery as shown in FIG. 5, which has an impermeable contact member. Thus, the curing system is generally designated by the reference numeral 80. In such a case, the hardened material covers the top and side contact members of the cell. This hardening material advantageously fills the intermediate space between layer 41 and support 50, as well as the openings in the support. To illustrate this filling, the various zones occupied by the hardened material are shown in Figs. In this case, the reference numeral 80 is used multiple times.

[0090] Also, the cured material may be applied to the cell of FIG. 6 having non-impermeable contact members, not shown. In such a case, the hardening material may be added to the top and side edges to form additional encapsulation. The hardened material covers the open spaces 53, 54 and the layers 41 and support 50. It should be noted that the encapsulation material 45 in the intermediate space between the be.

[0091] The stiffening system 80 may be made from any material that provides this mechanical stiffening function. With this in mind, for example, simple polymers or polymers filled with inorganic fillers can be used. The polymer matrix can be selected from, for example, epoxy, The fillers may be from the family of acrylates, or fluorinated polymers, particles, It can be made of flakes or glass fibers.

[0092] Advantageously, this curing system 80 can provide additional moisture barrier functionality. Considering this, for example, by selecting a glass with a low melting point, mechanical strength can be ensured, This glass can provide an additional moisture barrier. , Bi2O3-B2O3, ZnO-Bi2O3-B2O3, TeO2-V2O5, or P It can be from the family of bO-SiO2.

[0093] Typically, the curing system 80 is much thicker than the encapsulation system. The minimum thickness of this curing system in the front cladding of the stack is given by the reference E80. Advantageously, this thickness E80 is comprised between 20 and 250 μm, typically The presence of additional curing systems provides additional benefits. Therefore, this curing system can be optionally combined with an additional gas barrier function. It also provides mechanical and chemical protection.

[0094] As described hereinabove, the integration of the battery into the support 50 of the present invention allows each unit star This can be achieved by individually placing the blocks on their supports. In this case, multiple cells are fabricated together, each with its own integrated support.

[0095] Taking this into consideration, the method for manufacturing such a device is shown in FIGS. Advantageously, a support frame 105 is used to form a plurality of supports 50. This frame 104, shown on a larger scale in FIG. 7, includes a peripheral boundary 150 and its associated Each of the preforms 151 can be used to manufacture one battery. In the example shown, there are 12 identical predictions divided into three lines and four columns. Alternatively, a frame with a variable number of such preforms can be used. It can be used.

[0096] Each preform has a central region 155 that is used to form the base plate 55, and and two side blocks 156 used to form the strips 56, 57, respectively. , 157. The regions and blocks include grooves used to form the voids 53, 54. The separate preforms are separated from each other by separate horizontal bars 153 and 154. The vertical bar 158 and the vertical bar 159 provide support both to each other and to the peripheral edge. and fixed in place.

[0097] In this embodiment, each preform 151 is an already encapsulated preform such as that shown in FIG. In the manufacturing process, a quantity of non-conductive adhesive 106 is applied to form layer 6. The conductive adhesive is deposited on each area 155 so that the amount of conductive adhesive applied is equal to the amount of adhesive applied to the pad 30. , 31. The encapsulated stack is then covered with an adhesive layer 60 and a pad. The stack is then placed in contact with the supports to form grooves 30, 31. Fix it in place.

[0098] Finally, as shown in FIG. 9, the various components of the multiple cells are stacked on a frame 150. The various cutting lines are shown as dotted lines and the cutouts in the longitudinal dimension of the battery are marked with the reference D The cutout in the horizontal dimension is given the reference symbol D'. It should be noted that in the Act, the prescribed zones R and R' are intended to be abandoned. It is necessary.

[0099] In another embodiment not shown, the electrochemical device of the present invention may further comprise one or more Such components may include, for example, LDOs ("low dropout Typically, it can be of the miniaturized type with complex electronic functions. In this regard, the creation of a RTC ("Real Time Clock") circuit is possible. A module or energy harvesting module can be used. In this configuration, the unit stack is advantageously protected by the same encapsulation system that protects the unit stack. Covers more than one electronic component.

[0100] During operation, electrical energy is stored in the unit stack, as in the conventional method. , the conductive region 55 of the support 50 via the contact members and the conductive bonding pads 30, 31; 56. These conductive areas are insulated from each other, so there is no risk of short circuits. This electrical energy can then be transferred from the regions 56, 57 to any suitable type of energy source. Directed to the consuming device.

[0101] This energy consuming device is shown diagrammatically in FIG. 10 and is designated by the reference numeral 1000. It includes a body 1002 on which the underside of the support rests. The device 1 and the holder 50 are fixed to each other by any suitable means. 000 incorporates the battery shown in FIG. 5, whose contact members are impermeable. It should be noted that in another embodiment not shown, the battery of FIG. In such a case, the above-described The additional encapsulation material 45 makes the anode and cathode unit stack completely impermeable so that In this regard, it is necessary to ensure that the various positions of the reference numeral 45 in FIG. Reference is made to the above statements herein regarding

[0102] The device 1000 includes an energy consuming element 1004 and a support 5 for the element 1004. The wiring 1006 and 1007 electrically connect the regions 56 and 57 of the wiring 1006 and 1007. The control of the battery may be by components of the battery itself and / or by components (not shown) belonging to the device 1000. Non-limiting examples of such energy consuming devices include: Amplification type electronic circuits, clock type electronic circuits (real-time clock (RTC) components, etc.) volatile memory type electronic circuits, static random access memory (SRAM) type Electronic circuits, microprocessor-type electronic circuits, watchdog timer-type electronic circuits , LCD display type components, LED (light emitting diode) type components, voltage regulators electronic circuits (such as low dropout regulator circuits (LDO)) or CPU (medium The electronic component may be a central processing unit (Central Processing Unit) type electronic component.

[0103] Here, in contrast to the support 50 described above, the conductive support 750 is of the single layer type. Another embodiment, which is of the multi-layer type, is described with reference to Figures 11 and 12. In addition, the support 750 is of the perforated type, and is made of the metal described hereinabove. As shown in FIG. 11, the support 750 is a solid type, as opposed to a lattice. , for example, made of polymeric materials. These layers are stacked one on top of the other. the main plane of which is substantially the same as the plane of the layers forming the stack 1 described herein above. Therefore, the structure of this support is similar to that of a printed circuit board (PCB). is the same as:

[0104] 11 and 12 show, from top to bottom, the layers 756 that make up the stack of cells. This layer 756, which is primarily made of a polymer material such as vinyl resin, contains two inserts 7 57 are provided. These are made of a conductive material, in particular a metallic material, and are used as the anode of the battery. The contacts are designed to operate in conjunction with the corresponding cathode contacts. The inserts 757 are insulated from each other by the epoxy resin of layer 756. It is necessary to keep in mind that.

[0105] Immediately below layer 756 is layer 758, also made from a polymer material such as epoxy resin. This layer 758 is made of a conductive material that is in electrical contact with the first insert 757. Two inserts 759 are fabricated. These inserts 759 are located in the layer 75 6, are insulated from each other.

[0106] And there is an intermediate layer 760 which is significantly different from layers 756 and 758 described herein above. More specifically, this layer 760 typically comprises the insert 7 described hereinabove. This layer is made of a conductive material similar to that forming 57 and 759. , in particular two ring-shaped inserts made from epoxy resin as described herein above 761. These inserts 761 are connected to the adjacent conductive inserts 759. A disk 762 made of conductive material is placed in contact with the hollow center of the disk. These conductive disks 762 are insulated from each other via the ring 761. It is important to note that it is bounded.

[0107] Finally, layers 758 and 756, respectively, are identical to those described hereinabove in FIGS. There are twelve bottom layers 764 and 766. Layer 764 is the two layers that contact disk 762. The bottom layer 766 is provided with an insert 765, while the bottom layer 766 has two contacting layers 766a and 765b. There are provided three inserts 767. Various conductive inserts 757, 759, 76 2, 765, and 767 electrically connect the opposing end surfaces of the support portion 705. These paths define conductive paths shown by layers 756, 758, 759, and 760. 64 and 766 or by the disk 761.

[0108] In this embodiment, the curing system is the same as curing system 80 in the first embodiment. The protective film 780 can be deposited in particular by a lamination step. Such membranes with rear properties are, for example, polyethylene terephthalate membranes incorporating inorganic multilayers. One such product made from polyethylene terephthalate (PET) that may be suitable for this application is Ultra Barr. ier Film 510 or Ultra Barrier Solar Film 5 It is commercially available from 3M under the reference name 10-F. However, films obtained by rolling Such curing systems using fluorine may be used for other applications in addition to those shown in Figure 11. can be done.

[0109] FIG. 11 shows the support 705, stack 702, conductive pads 730, 740, and encapsulation 70. 7 and membrane 708 into the energy consuming device 1000. In this embodiment, the energy generated in the stack 702 is transferred to the contact members 73 0, 740 to the upper insert 757. This energy is then transferred to the to the energy consuming device 1000 along the connection paths 753, 754 described herein above. It is transmitted.

[0110] In its most common construction, a multi-layer support consists of only two separate layers, one above the other. These layers may be formed from the same conductive paths 753, 754 described herein above. This particular embodiment shown with respect to Figure 11 has certain advantages. More specifically, a multi-layer support such as that shown by reference numeral 750 advantageously comprises 100 The support has an extremely small thickness of less than 1 μm. The joining benefits from particularly good bending strength.

[0111] The present invention is not limited to the examples described and illustrated.

[0112] In a first alternative embodiment not shown, each current collecting substrate may be perforated. Advantageously, each perforation (or opening) The lateral dimensions of the holes are between 0.02 mm and 1 mm. The porosity is between 10% and 30%. This means that for a given surface area of ​​this substrate, This means that perforations account for 10% to 30% of the surface area.

[0113] The technical purpose of these perforations or openings is to allow a first layer deposited on one of the two faces of the substrate to The first layer is then bonded to the other of the two surfaces of the substrate in the opening. This improves the quality of the deposition, especially the adhesion of the layer in contact with the substrate. During the sintering operation, the layers mentioned above shrink slightly, i.e., their longitudinal and lateral dimensions The dimensions of the substrate remain essentially unchanged while the size of the substrate is slightly reduced. The interface is prone to shear stress, thus reducing the quality of the bond. As is increased, this stress increases.

[0114] Under these conditions, the provision of a perforated substrate significantly improves the quality of this adhesion. In effect, the layers located on opposite sides of the substrate tend to weld together within the various perforations. This allows for a large layer deposition thickness even if the layer does not contain any organic binder after annealing. This alternative embodiment also allows for increased battery output. This is particularly well suited for use with thick mesopore-type ultra-high power electrodes. do.

[0115] The method of the present invention is particularly useful for solid-state batteries, i.e., batteries in which the electrodes and electrolyte are solid and the solid phase This is suitable for the manufacture of batteries that do not even contain a liquid phase impregnated in the battery.

[0116] The method according to the invention is particularly directed to a method comprising the steps of: This standard is suitable for the manufacture of batteries that are considered quasi-solid-state.

[0117] The separator described above preferably comprises: - More than 30%, preferably between 35% and 50%, more preferably 40% % to 50% porosity, preferably mesopores, - Mean diameter D less than 50 nm 50 It is a porous inorganic layer having pores.

[0118] It is understood that the separator is often sandwiched between the electrodes. In an embodiment, this is deposited on at least one of the electrodes to create a solid assembly of the battery. The separator is a ceramic or glass-ceramic filter that is laminated and sintered. The nano-compression within the rotor gives the final battery quasi-solid-state properties.

[0119] The thickness of the separator is chosen to minimize the final thickness of the battery without compromising its performance. Advantageously, it is less than 10 μm, preferably between 3 μm and 16 μm, more preferably 3 μm The separator is preferably between 2.5 μm and 6 μm, and more preferably between 2.5 μm and 4.5 μm. The pores of the electrode are filled with an electrolyte, preferably a liquid electrolyte containing a lithium salt or an ionic liquid. The lithium ion-carrying phase is impregnated in the pores, especially the mesopores. or "nano-trapped" liquid cannot escape. This is referred to herein as "meso-trapped" liquid. This is due to a phenomenon called "pore structure absorption" (described in the literature within the context of lithium-ion batteries). It is not possible to escape even when the cell is placed in a vacuum. Therefore, such batteries are considered quasi-solid-state batteries.

[0120] The method and encapsulation system of the present invention is particularly suitable for any type of thin film battery, and in particular for any This can be applied to the following types of lithium-ion batteries.

[0121] This lithium-ion battery is a solid-state multilayer lithium-ion battery, a quasi-solid-state multilayer lithium-ion battery, The battery may be a lithium-ion battery, in particular a solid-state multilayer lithium-ion microbattery. More generally, this lithium-ion battery, especially within the scope of microbatteries, is internationally recognized. an anode layer, an electrolyte layer, and a catalyst layer, such as those described in Publication No. 2013 / 064777; The cathode layer, i.e., the layer made of one or more of the materials according to claim 13 of this document. a cathode layer made of one or more of the materials according to claim 14 of this document, and the use of an electrolyte layer made from one or more of the materials according to claim 15 of this document. can be done.

[0122] The battery in the present invention may be a lithium ion micro battery, a lithium ion mini battery, or It can be a high-power lithium-ion battery. In particular, it can have a capacity of about 1 mAh or less. (commonly known as "microbatteries"), exceeding about 1 mAh and reaching about 1 Ah (commonly known as "mini batteries"), or greater than about 1Ah (commonly known as "high power batteries") Typically, microbatteries are designed to be compatible with microelectronics manufacturing methods. It is designed to be like this.

[0123] The batteries in each of these three power ranges are: - "Solid" type layers, i.e. impregnated liquid or paste phases (the liquid or paste phases (can be a lithium ion conducting medium that can act as an electrolyte) No layers, - Or, the layer may spontaneously permeate, so that the layer can be considered a quasi-solid. A liquid or paste phase, typically impregnated with a lithium ion conducting medium, from which neither the lithium ion nor the lithium ion can escape. a "solid" type layer of mesopores, - or an impregnated porous layer (i.e. containing a liquid or paste phase that gives this layer wetting properties) The layer may be made of a material having a network of open pores that is permeable.

Claims

1. A battery, - anode current collecting substrate, anode layer, layer of electrolyte material or separator impregnated with electrolyte At least one unit cell comprising, in sequence, a cathode layer, a cathode layer, and a cathode current collecting substrate. and if the battery includes multiple unit cells, the second one is in the layer order shown. a unit cell disposed on top of the first one, etc.; the periphery of said unit cell, or of all said unit cells if there are several; Covering at least a portion of Optionally, but preferably, parylene, parylene F, polyimide, epoxy resin, silicone a polyamide, a sol-gel silica, an organosilica, and / or a mixture thereof; a first coating layer deposited on the battery; - optionally made of an electrically insulating material and applied to said cell or to said first coating layer by atomic layer deposition; a second coating layer deposited by - a small number of electrodes used to make electrical contact between at least said unit cells and external conductive elements; at least one anode contact member; - at least one cathode core used to make electrical contact with an external conductive element; and a contact member, the battery includes a first contact surface defining at least one anode connection zone; the cell includes a second contact surface defining at least one cathode connection zone; The encapsulation system comprises: -10 －５ g / m ２ d or less, and the ceramic material and / or made from low-melting glass, preferably glass having a melting point below 600°C. and at least a third impermeable coating layer deposited on the outer periphery of the battery or the first coating layer. Including, When the second coating layer is present, a series of the second coating layer and the third coating layer is formed z times. It can be repeated, z≧1, and deposited on at least the outer periphery of the third coating layer, The final layer of the encapsulation system is made of a ceramic material and / or a low-melting glass. 0 －５ g / m ２ The impermeable coating layer has a water vapor transmission rate (WVTR) of less than . ,battery.

2. Preferably 10 －５ g / m ２ The third non-woven fabric has a water vapor transmission rate (WVTR) of less than . The permeable coating layer has a thickness of 1 μm to 50 μm, more preferably 1 μm to 10 μm, and even more preferably 2. The battery according to claim 1, having a thickness comprised between 1 μm and 5 μm.

3. Each of the anode contact member and the cathode contact member is - arranged at least in the anode connection zone and at least in the cathode connection zone and a material filled with electrically conductive particles, preferably a polymer filled with electrically conductive particles. Resin and / or sol-gel derived materials, more preferably graphite filled a first electrical connection layer comprising a polymer resin; a second electrical connection comprising a metal foil disposed on said first layer of material filled with electrically conductive particles; 3. The battery of claim 1 or 2, comprising a layer.

4. the metal foil is of the free-standing type and is advantageously attached to the first electrical connection layer, The battery according to any one of claims 1 to 3.

5. 5. The method according to claim 1, wherein the metal foil is produced by rolling or electroplating. Battery as described.

6. The thickness of the metal foil is comprised between 5 and 200 micrometers, and the metal foil is particularly , nickel, stainless steel, copper, molybdenum, tungsten, vanadium, tantalum, titanium made from one of the following materials: tungsten, aluminum, chromium, and alloys containing them; The battery according to any one of claims 1 to 5.

7. Each of the anode contact member and the cathode contact member is 7. The method according to claim 1, further comprising a third layer comprising a conductive ink disposed on the electrical connection layer. On-board battery.

8. - an electrode made at least in part from a conductive material and provided near the end face of the unit cell; Air connection support, - two separate areas of the connection support, each forming an electrical connection path, are separated from each other; Electrical insulating means capable of insulating, - the annulus capable of electrically connecting the first side of each unit cell to a first electrical connection path; and electrically connecting the second side of each unit cell to the second electrical connection path. The cathode contact member according to any one of claims 1 to 7, further comprising: battery.

9. The electrical connection support is of the single-layer type, in particular a metal grid or a silicon intermediate layer; The battery according to any one of claims 1 to 8.

10. The electrical connection support comprises a plurality of layers arranged one above the other, in particular a printed circuit board.

9. The battery of claim 8, which is of the type

11. The impermeable coating layer is preferably formed on each of the anode contact members and the cathode contact members. the primary impermeable coating layer, which does not cover the contact elements, and in particular all of the contact elements; or partly covering the electrical connection support, and in particular at least partly covering the electrical connection support. The battery of any one of claims 8 to 10, comprising a permeable coating layer.

12. The battery according to any one of claims 1 to 11, which is a lithium ion battery.

13. The battery of any one of claims 1 to 12, which is a solid-state lithium-ion battery.

14. Any one of claims 1 to 13, designed and configured to have a capacity of 1 mAh or less. Any battery described above.

15. Any of claims 1 to 14, designed and configured to have a capacity of more than 1 mAh. The battery described in any one of the preceding claims.

16. A method for producing a battery according to one of claims 1 to 15, comprising the steps of: (a) coated with an anode layer and optionally impregnated with a layer of electrolyte material or electrolyte; At least one anode foil, hereinafter referred to as the anode foil, is coated with a layer of a separator having a thickness of 1000 .mu.m or less. providing an anode current collecting substrate foil; (b) coated with a cathode layer and optionally impregnated with a layer of electrolyte material or electrolyte; at least one cathode foil, hereinafter referred to as the cathode foil, coated with a layer of a separator providing a cathode current collecting substrate foil; (c) at least one anode current collecting substrate, at least one anode layer, and an electrolyte material; At least one layer of separator impregnated with a material or electrolyte, at least one cathode and at least one cathode current collecting substrate. Step of preparing a stack (I) of alternating node foils and at least one cathode foil. P, (d) combining the alternating layers obtained in step (c) to form a consolidated stack. heat treating and / or mechanically compressing said stack of foils, (e) - optionally, preferably parylene, parylene F, polyimide, epoxy resin; silicone, polyamide, sol-gel silica, organosilica, and / or mixtures thereof At least one first coating layer in the battery is selected; - optionally made of an electrically insulating material and applied to said cell or to said first coating layer by atomic layer deposition; a second coating layer deposited on the substrate; and - preferably 10 －５ g / m ２ It has a water vapor transmission rate (WVTR) of less than . from a glass material and / or a low melting point glass, preferably a glass having a melting point below 600°C. and at least a third impermeable coating layer is fabricated and deposited on the outer periphery of the battery or the first coating layer. encapsulating the integrated stack by depositing a covering layer; This sequence of at least one second coating layer and at least one third coating layer is z may be repeated 100 times, z≧1, and deposited on at least the outer periphery of the third coating layer; the final layer of the encapsulation system is made of a ceramic material and / or a low-melting glass; 10 －５ g / m ２ The impermeable coating layer has a water vapor transmission rate (WVTR) of less than 1.5 d. ru, step, (f) exposing at least the anode connection zone and the cathode connection zone. The step of making two cutouts (Dn, D'n) to form a cut stack. P, (g) fabricating an anode contact member and a cathode contact member. Hmm, a method.

17. The anode contact member and the cathode contact member are fabricated by: - made from a material filled with electrically conductive particles, preferably filled with electrically conductive particles The first electrical contact is made of a polymer resin and / or a material obtained by a sol-gel method. a connecting layer at least in the anode connection zone and at least in the cathode connection zone, Preferably, at least the contact surface and at least the anode connection zone are depositing at least on said contact surface including at least said cathode connection zone; Optionally, the first layer is made of a polymeric resin and / or sol-gel filled with electrically conductive particles. When the polymer resin is prepared from a material obtained by the PET process, a drying step is performed, followed by the step of and / or polymerizing the sol-gel derived material, a second electrical connection layer, preferably a metal foil or a metal ink, disposed on said first electrical connection layer; A connecting layer is deposited on the first layer, and in the latter case the drying step is also performed on the second electrical 17. The method of claim 16, comprising: performing the method after deposition of the connecting layer.

18. The metal foil is formed by rolling, and then the metal foil thus formed is 18. The method according to claim 16 or 17, wherein the first electrical connection layer is applied.

19. The metal foil is either ex situ or in situ bonded to the first metal connection layer.

18. The method according to claim 16 or 17, wherein the material is directly formed by electroplating.

20. The method further comprises, after step (g), coating the substrate with the first electrical connection layer and the second electrical connection layer. At least the anode connection zone and the cathode connection zone of the battery are connected to the 20. The method of claim 16, further comprising the step (h) of depositing a conductive ink.

1. The method according to claim 1.

21. The low-melting glass is SiO ２ -B ２ O ３ , Bi ２ O ３ -B ２ O ３ , ZnO-Bi ２ O ３ -B ２ O ３ , TeO ２ -V ２ O ５ , and PbO—SiO ２ 16. The compound according to claim 15, 20. The method according to claim 1,

22. The second coating layer is deposited at low temperature by PECVD, preferably HDPCVD or ICP. The method according to one of claims 16 to 21, deposited by CVD.

23. The second coating layer is an oxide and / or nitride and / or Ta. ２ O ５ and / or oxynitrides and / or Si ｘ N ｙ and / or SiO ２ and / or SiON and / or amorphous silicon and 23. The method according to claim 16, further comprising the step of: forming a ceramic substrate using a ceramic material containing silicon dioxide;

24. The impermeable sealing means positions the electrical connection support portion near the first end surface of the unit stack.

16. The method for producing a battery according to claim 8, wherein the battery is coated after The method according to any one of claims 16 to 23.

25. At least a part of the impermeable sealing means is arranged to connect the electrical connection support to the first one of the unit stacks. The electrode according to any one of claims 8 to 15, which is coated before being placed near one end face. A method according to one of claims 16 to 23 for creating a pond.

26. At least the first impermeable coating layer supports the electrical connection support portion of the unit stack. before being placed near one end face, and then the further impermeable coating layer is applied to the The electrical connection support is coated after being disposed near the first end surface. The method according to any one of claims 16 to 25 for producing a battery according to any one of claims 15. method.

27. - providing a frame (105) which is used to form a plurality of supports (5); and, - first end faces of a plurality of unit stacks arranged in a plurality of lines and / or a plurality of rows; placing the frame adjacent to the - longitudinally and / or laterally extending the stack to form a plurality of electrochemical devices; making at least one cutout, in particular a plurality of cutouts, in the direction The method according to one of claims 16 to 26.

28. An electric energy consuming device (1000) comprising a body (1002) and 16. The method according to claim 1, wherein the method is capable of supplying electrical energy to an energy consuming device. and a battery mounted thereon, wherein the electrical connection support (5) of the battery is fixed to the body. An energy consuming device (1000).

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