Batteries with encapsulation systems

Abstract

This invention relates to batteries, and in particular to thin-film batteries including novel packaging systems.

Description

Technical Field

[0001] This invention relates to batteries, particularly thin-film batteries, and more specifically, to encapsulation systems for protecting batteries. More specifically, this invention relates to the field of lithium-ion batteries that can be encapsulated in this manner. The invention also relates to a novel method for manufacturing thin-film batteries with a novel structure and encapsulation, resulting in particularly low self-discharge rates and longer lifespans. Background Technology

[0002] Because oxygen and moisture can degrade battery performance, certain types of batteries, especially some types of thin-film batteries, require encapsulation to achieve a longer lifespan. Lithium-ion batteries, in particular, are highly sensitive to moisture. The market demands a product lifespan of over 10 years; therefore, encapsulation is essential to ensure this lifespan requirement is met.

[0003] Thin-film lithium-ion batteries are multilayer stacks comprising electrodes and electrolyte layers, typically with a thickness of approximately 1 µm to approximately 10 µm. They can comprise stacks of multiple cell units. These batteries are considered highly sensitive to self-discharge. Depending on the location of the electrodes, particularly their distance from the edges of the multilayer cell electrodes and the cleanliness of the cuts, leakage current can occur at the ends, resulting in creepage short circuits that degrade battery performance. This phenomenon is exacerbated if the electrolyte membrane is very thin.

[0004] These solid-state thin-film lithium-ion batteries typically use an anode with a lithium metal layer. During charge and discharge cycles, a significant volume change in the anode material can be observed. More specifically, during charge and discharge cycles, some lithium metal is converted into lithium ions, which are then embedded into the structure of the cathode material, resulting in a decrease in anode volume. This periodic volume change deteriorates the mechanical and electrical contact between the electrode and electrolyte layers. This reduces the battery's performance over its lifespan.

[0005] Periodic changes in the volume of the anode material also cause periodic changes in the volume of the cell. This generates periodic stress in the packaging system, which can easily lead to cracking and loss of impermeability (or even integrity) of the packaging system. This phenomenon is yet another reason for battery performance degradation during its lifespan.

[0006] More specifically, the active materials in lithium-ion batteries are highly sensitive to air, especially moisture. Migrating lithium ions spontaneously react with trace amounts of water to form LiOH, leading to premature aging of the battery. All lithium-ion conductive electrolytes and intercalation materials do not react with moisture. For example, Li₄Ti₅O₂... 12 Its performance does not degrade upon contact with the atmosphere or trace amounts of water. In contrast, once Li... 4+x Ti5O 12Lithium is filled in a form where x>0. The remaining lithium (x) inserted is sensitive to the atmosphere and spontaneously reacts with trace amounts of water to form LiOH. Therefore, the lithium remaining after the reaction can no longer be used to store electricity, resulting in a loss of battery capacity.

[0007] To prevent the active materials of lithium-ion batteries from coming into contact with air and water, and to prevent such aging, they must be protected using an encapsulation system. Many encapsulation systems for thin-film batteries are described in the literature.

[0008] US Patent No. 2002 / 0071989 describes a packaging system for solid-state thin-film batteries, comprising a first dielectric material layer selected from alumina (Al2O3), silicon dioxide (SiO2), silicon nitride (Si3N4), silicon carbide (SiC), tantalum oxide (Ta2O5), and amorphous carbon, a second dielectric material layer, and a stack of an impermeable sealing layer disposed on the second layer and covering the entire battery.

[0009] US Patent No. 5561004 describes several systems for protecting thin-film lithium-ion batteries. The first proposed system includes a parylene layer covering an aluminum film deposited on the battery's active components. However, this system, which prevents the diffusion of air and water vapor, is only effective for about a month. The second proposed system includes alternating parylene layers (500 nm thick) and metal layers (approximately 50 nm thick). The document indicates that it is preferable to further coat these batteries with a UV-cured epoxy resin coating to reduce the rate at which the batteries are degraded by atmospheric factors.

[0010] The applicant also proposed examples in international patent document WO 2019 / 215410 of layers intended to form anode and cathode contact elements, respectively. In a first example, the first thin layer is deposited by ALD and is specifically a metal layer. Furthermore, a second silver-filled epoxy resin layer is provided. In a second example, the first layer is a graphite-filled material, while the second layer comprises copper metal obtained from nanoparticle-filled ink.

[0011] According to existing technology, most lithium-ion batteries are encapsulated in metallized polymer foil (referred to as a "bag"), which surrounds the battery cell and is heat-sealed at the connector tabs. These encapsulations are relatively flexible, allowing the positive and negative terminals of the battery to be embedded in the heat-sealed polymer used to seal the encapsulation around the battery. However, this welding between the polymer foils is not entirely impermeable to atmospheric gases, as atmospheric gases are relatively permeable to the polymer of the heat-sealed battery. Permeability increases with increasing temperature, thus accelerating aging.

[0012] However, the surface area of ​​these weld seams exposed to the atmosphere is still very small, and the remaining encapsulation is formed by aluminum foil sandwiched between these polymer foils. Typically, two aluminum foils are combined to minimize the impact of the presence of holes, which constitute defects in each of these foils. The probability of two defects aligning on each strip is greatly reduced.

[0013] These encapsulation technologies ensure that, under normal operating conditions, the surface area is 10 x 20 cm. 2 A 10 Ah battery has a calendar life of approximately 10 to 15 years. If the battery is exposed to high temperatures, this lifespan can be reduced to less than 5 years, which is insufficient for many applications. Similar techniques can be used in other electronic components, such as capacitors and active components.

[0014] Therefore, systems and methods are needed for encapsulating thin-film batteries and other electronic components to protect them from the effects of air, moisture, and temperature. The encapsulation system must be impermeable and sealable, completely encapsulating and covering the component or battery, and must also allow for electrical isolation between electrode edges of opposite polarities to prevent any creepage short circuits.

[0015] One object of the present invention is to overcome at least some of the deficiencies of the prior art described above.

[0016] Another object of the present invention is to provide a lithium-ion battery with a very long lifespan and a low self-discharge rate. Summary of the Invention

[0017] The packaging system described in this invention is preferably of a rigid type. Due to the initially selected materials, the battery cell is rigid and dimensionally stable. Therefore, the packaging system obtained according to this invention is effective.

[0018] This invention provides a packaging system for production that can, and preferably, be deposited in a vacuum. The batteries described in this invention do not contain polymers; however, they may contain ionic liquids. More specifically, they are solid or "quasi-solid" type, in which case they comprise an electrolyte based on a nano-confined ionic liquid. From an electrochemical perspective, this nano-confined liquid electrolyte behaves like a liquid because it provides good flowability for the cations that conduct electricity therefrom. From a structural perspective, this nano-confined liquid electrolyte does not behave like a liquid because it remains nano-confined and can no longer escape even when treated in a vacuum and / or at high temperatures.

[0019] The batteries comprising a nano-confined ion liquid-based electrolyte described in this invention can therefore be encapsulated by vacuum processing and / or by vacuum and high-temperature processing. To allow impregnation before encapsulation, the edges of the individual layers can be exposed by cutting; after impregnation, these edges are sealed by making electrical contacts. The method described in this invention is also highly suitable for covering mesoporous surfaces.

[0020] The method described in this invention is also very suitable for covering mesoporous surfaces.

[0021] At least one of the above objectives is achieved by at least one objective of the present invention as described below.

[0022] The first objective of this invention is to provide a battery comprising:

[0023] - At least one cell, which sequentially comprises an anode current collector substrate, an anode layer, an electrolyte material layer or an electrolyte-impregnated separator layer, a cathode layer, and a cathode current collector substrate.

[0024] It is important to remember that, in the case where the battery comprises multiple cell units, the second cell unit is placed on top of the first cell unit in the layered order shown, and so on.

[0025] - A packaging system that covers the periphery of the cell unit or, in the presence of multiple cell units, covers at least a portion of the periphery of all cell units, the packaging system comprising:

[0026] The first coating layer optionally deposited on the battery is preferably selected from parylene, parylene F, polyimide, epoxy resin, silicone resin, polyamide, sol-gel silica, organosilicon silica and / or mixtures thereof.

[0027] A second cover layer, composed of an electrically insulating material, may be optionally deposited on the battery or the first cover layer using atomic layer deposition.

[0028] - At least one anode contact element designed to form an electrical contact between the at least one cell and an external conductive element, the cell including a first contact surface defining at least one anode connection region, and

[0029] - At least one cathode contact element designed to enable electrical contact with an external conductive element, the battery including a second contact surface defining at least one cathode connection region.

[0030] The battery is characterized in that the packaging system further includes:

[0031] - At least a third impermeable capping layer with a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 .d, the third capping layer is made of ceramic material and / or low-melting-point glass, preferably glass with a melting point below 600°C, and the layer is deposited around the battery or the first capping layer.

[0032] It should be understood that, when the second capping layer is present, the sequence of the second and third capping layers can be repeated z times, where z ≥ 1, and deposited at least around the third capping layer. It should also be understood that the final layer of the encapsulation system is the impermeable capping layer with a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 .d, made of ceramic materials and / or low-melting-point glass.

[0033] Other features of the battery described in this invention may be individual features or any technically compatible features:

[0034] - A third impermeable capping layer, preferably with a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 .d, with a thickness between 1 μm and 50 μm, more specifically between 1 μm and 10 μm, and even more specifically between 1 µm and 5 µm.

[0035] - Each anode contact element and cathode contact element includes:

[0036] A first electrical connection layer is disposed on at least an anode connection region and at least a cathode connection region. This first electrical connection layer comprises a material filled with conductive particles, preferably a polymer resin filled with conductive particles and / or a material obtained by a sol-gel method, more preferably a polymer resin filled with graphite.

[0037] The second electrical connection layer includes a metal foil disposed on a first material layer filled with conductive particles.

[0038] - The metal foil is of the self-supporting type, and the metal foil is preferably applied to the first electrical connection layer;

[0039] - The metal foil is prepared by rolling or electroplating;

[0040] - The thickness of the metal foil is between 5 and 200 micrometers, and the metal foil is made in particular from one of the following materials: nickel, stainless steel, copper, molybdenum, tungsten, vanadium, tantalum, titanium, aluminum, chromium and alloys containing them;

[0041] - Each of the anode contact element and the cathode contact element includes a third layer, the third layer including conductive ink disposed on the second electrical connection layer;

[0042] - The battery also includes:

[0043] An electrical connection support made at least partially of a conductive material, the support being disposed near the end face of the cell;

[0044] An electrical insulation device enables two distant regions of the connecting support to be insulated from each other, these distant regions forming their own electrical connection paths.

[0045] - The anode contact element enables a first side of each cell to be electrically connected to a first electrical connection path, while the cathode contact element enables a second side of each cell to be electrically connected to a second electrical connection path.

[0046] - The electrical connection support is of a single-layer type, particularly a metal mesh or silicon sandwich;

[0047] - The electrical connection support includes multiple layers, with one layer disposed below another, and the support is particularly of the printed circuit board type;

[0048] - The impermeable covering layer includes a first impermeable covering layer, particularly not covering the anode contact element and the cathode contact element respectively, and other impermeable covering layers, particularly covering all or part of the contact elements, particularly at least partially covering the electrical connection support.

[0049] - The battery is a lithium-ion battery.

[0050] - It is a solid-state lithium-ion battery.

[0051] - It was designed and sized to have a capacity of less than or equal to 1 mAh.

[0052] - It was designed and sized to give it a capacity greater than 1 mAh.

[0053] The present invention also relates to a method for manufacturing the above-mentioned battery, the manufacturing method comprising:

[0054] a) Provide at least one anode current collector substrate foil, said anode current collector substrate foil being coated with an anode layer and optionally coated with an electrolyte material layer or an electrolyte-impregnated insulating layer, hereinafter referred to as the anode foil.

[0055] (b) Provide at least one cathode current collector substrate foil, said cathode current collector substrate foil being coated with a cathode layer and optionally coated with an electrolyte material layer or an electrolyte-impregnated insulating layer, hereinafter referred to as cathode foil.

[0056] c) Prepare an alternating stack (I) of at least one anode foil and at least one cathode foil to sequentially obtain at least one anode current collector substrate, at least one anode layer, at least one electrolyte material layer or an electrolyte-impregnated isolation layer, at least one cathode layer, and at least one cathode current collector substrate.

[0057] d) The alternating foil stacks obtained in step c) of heat treatment and / or mechanical compression form a stable stack.

[0058] e) Perform the step of encapsulating the robust stack by depositing the following layers:

[0059] - Optionally, at least one first covering layer on the battery, preferably selected from parylene, parylene F, polyimide, epoxy resin, silicone resin, polyamide, sol-gel silica, organosilicon silica and / or mixtures thereof.

[0060] - An optional second capping layer, composed of an electrically insulating material, is deposited on the battery or the first capping layer using atomic layer deposition.

[0061] - At least one third impermeable covering layer, preferably with a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 .d, the third capping layer is made of ceramic material and / or low-melting-point glass, preferably glass with a melting point below 600°C, and is deposited around the battery or the first capping layer.

[0062] It should be understood that the sequence of the at least one second capping layer and the at least one third capping layer can be repeated z times, where z≥1, and deposited on the periphery of the at least third capping layer, with the final layer of the encapsulation system being the impermeable capping layer having a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 .d, made of ceramic materials and / or low-melting-point glass.

[0063] f) Create two cuts (Dn, D'n) to form a cut stack that exposes at least the anode connection region and the cathode connection region;

[0064] g) Prepare anode contact elements and cathode contact elements.

[0065] Other features of the method described in this invention may be individual features or any technically compatible features:

[0066] - The fabrication of anode contact elements and cathode contact elements includes:

[0067] A first electrical connection layer, preferably made of a material filled with conductive particles, is deposited on at least the anode connection region and at least the cathode connection region, preferably on at least the contact surface including the at least anode connection region and at least on the contact surface including the at least cathode connection region. The first electrical connection layer is preferably made of a polymer resin filled with conductive particles and / or a material obtained by a sol-gel method.

[0068] Optionally, when the first layer is made of a polymer resin filled with conductive particles and / or a material obtained by the sol-gel method, the step of polymerizing the polymer resin and / or the material obtained by the sol-gel method is performed after the drying step.

[0069] A second electrical connection layer is deposited on the first electrical connection layer. The second electrical connection layer is preferably a metal foil or a metallic ink. It should be noted that, in the latter case, the drying step may be performed after the deposition of the second electrical connection layer.

[0070] - The metal foil is formed by rolling, and then the metal foil thus formed is applied to the first electrical connection layer.

[0071] - The metal foil is formed directly by electroplating, either in situ or off-site relative to the first metal bonding layer.

[0072] - Following step g), the method includes step h) depositing conductive ink on at least the anode connection region and the cathode connection region of the battery coated with the first and second electrical connection layers.

[0073] - Low-melting-point glasses are selected from SiO2-B2O3, Bi2O3-B2O3, ZnO-Bi2O3-B2O3, TeO2-V2O5, and PbO-SiO2.

[0074] - The second capping layer is deposited at low temperature by PECVD, preferably by HDPCVD or ICP CVD.

[0075] - The second capping layer comprises oxides and / or nitrides and / or Ta2O5 and / or oxynitrides and / or Si x N y and / or SiO2 and / or SiON and / or amorphous silicon and / or SiC,

[0076] - Apply an impermeable sealant after placing the electrical connection support near the first end face of the unit stack.

[0077] - Apply at least a partially impermeable sealant before placing the electrical connection support near the first end face of the unit stack.

[0078] - Apply at least a first impermeable coating layer before placing the electrical connection support near the first end face of the unit stack, and then apply other impermeable coating layers after placing the electrical connection support near the first end face.

[0079] - Further details:

[0080] A frame (105) is provided for forming multiple support members (5).

[0081] The frame is placed near the first end face of a stack of multiple units arranged in multiple rows and / or columns.

[0082] At least one cut, and in particular multiple cuts, are formed in the longitudinal and / or transverse directions of these stacks, thereby forming multiple electrochemical devices.

[0083] Finally, the object of the present invention is an energy-consuming device, comprising a main body and the aforementioned battery, wherein the battery is capable of providing electrical energy to the energy-consuming device, and wherein the electrical connection support of the battery is fixed to the main body.

[0084] First, it should be pointed out that the applicant must recognize that the prior art has certain deficiencies in terms of impermeability. In particular, the applicant has observed that a critical region is formed at the interface between the encapsulation system and the contact element. Essentially, this region forms a preferred entry point for various components, especially water molecules, that may interfere with the proper operation of the electrodes. However, in the prior art, the aforementioned interface is unsatisfactory in terms of impermeability because it does not form a sufficient barrier against these components.

[0085] Conversely, the presence of the impermeable capping layer described in this invention overcomes the shortcomings of the prior art. More specifically, this capping layer defines a barrier layer that is particularly effective against the aforementioned harmful components. Furthermore, this capping layer preferably has a relatively large thickness. In this way, mechanical damage from deposits such as ALD formation can be prevented. The present invention thus provides a rigid and impermeable encapsulation, particularly preventing water vapor from passing through the interface between the encapsulation system and the contact elements.

[0086] In a particularly preferred manner, the battery of the present invention includes a metal foil in its second electrical connection layer. As understood within the scope of the invention, this metal foil preferably has an "auto-porteuse" type structure, or in English, a "free-standing" structure. In other words, it is produced "off-site" and then brought to the vicinity of the first layer above. The metal foil can be obtained, for example, by rolling; in this case, the rolled foil may undergo partial or complete final soft annealing.

[0087] The metal foil used in this invention can also be obtained by other methods, particularly by electrochemical deposition or electroplating. In this case, it can usually be done "ex-situ" as described above. Alternatively, it can be done "in-situ," that is, directly on the first layer above.

[0088] In any case, once produced, this metal foil has a controlled thickness.

[0089] It should be noted that the copper-containing metal layer obtained by nanoparticle-filled ink described in the aforementioned international patent document WO 2019 / 215410 is by no means a metal foil as understood within the scope of this invention. More specifically, the layer disclosed in that prior art document does not meet any of the above criteria.

[0090] Typically, the thickness of this metal foil is between 5 and 200 micrometers. Furthermore, the metal foil is preferably completely dense and conductive. As a non-limiting example, the metal foil can be made from materials such as nickel, stainless steel, copper, molybdenum, tungsten, vanadium, tantalum, titanium, aluminum, chromium, and alloys containing them.

[0091] Combining this metal foil with a coating enhances the aforementioned technical effects, particularly in terms of impermeability. It should be noted that the impermeability provided by this metal foil is significantly higher than that offered by deposited metal nanoparticles. More specifically, the sintered films contain more point defects, resulting in poorer sealing.

[0092] Furthermore, the surface of metal nanoparticles is typically covered with a thin oxide layer, the properties of which limit their conductivity. In contrast, the use of metal foil improves both hermeticity and conductivity.

[0093] Furthermore, the use of metal foil allows for the application of a wide range of materials. This ensures that the chemical compositions in contact with the anode and cathode, respectively, are electrochemically stable. In contrast, in existing technologies, the available materials for forming nanoparticles are relatively limited.

[0094] The drying step mentioned in the appended claims specifically ensures that the metal foil adheres to at least the anode connection area and / or at least the cathode connection area, preferably to at least the contact surface including at least the anode connection area and / or at least the contact surface including at least the cathode connection area. Attached Figure Description

[0095] The accompanying drawings schematically illustrate multilayer batteries encapsulated according to different embodiments of the present invention. They correspond to cross sections perpendicular to the layer thickness.

[0096] Figure 1 A battery comprising a single cell is shown; the packaging system comprises three distinct layers.

[0097] Figure 2 The diagram shows a stack comprising four cell units; the packaging system comprises three distinct layers.

[0098] Figure 3 The diagram shows a stack comprising four cell units; the packaging system consists of three consecutive, two distinct layers.

[0099] Figure 4A and Figure 4B A perspective view is shown of alternating stacks of anode and cathode foils included in two alternative embodiments of the battery manufacturing method described in this invention.

[0100] Figure 5 It shows Figure 1 A longitudinal cross-sectional view of the battery, further including conductive support components.

[0101] Figure 6 It shows Figure 5 A longitudinal cross-sectional view of an alternative embodiment of the shown example.

[0102] Figure 7 It shows that multiple can be produced simultaneously Figure 5 Or a top view of the frame of the battery described in 6.

[0103] Figure 8 Is with Figure 5 A similar front view shows the manufacturing process. Figure 5 The steps for the battery shown.

[0104] Figure 9 It shows Figure 7 A top view of multiple batteries is obtained by cutting within the frame.

[0105] Figure 10 It is Figure 5 A front view of a battery integrated into an energy-consuming device.

[0106] Figure 11 It is similar to Figure 10 The front view shows Figure 10 Alternative embodiments of the illustrated examples, particularly concerning the structure of the conductive support.

[0107] Figure 12 yes Figure 11 Exploded perspective view of different components of the central conductive support. Detailed Implementation

[0108] This invention applies to so-called unitary electrochemical cells, which are stacks comprising, in sequence, an anode current collector, an anode layer, an electrolyte material layer or an electrolyte-impregnated separator, a cathode layer, and a cathode current collector. The current collector is also referred to herein as a "current collector substrate," i.e., an anode current collector substrate and a cathode current collector substrate.

[0109] The present invention is further applicable to batteries comprising multiple stacked cell units.

[0110] The encapsulation that represents a key feature of the present invention is described herein.

[0111] After the stacking of the layers constituting the battery is fabricated, and after mechanical and / or thermal treatment steps to stabilize the stack (which can be hot pressing, including the simultaneous application of high pressure and high temperature), the stack is encapsulated by a deposition encapsulation system to protect the battery cells from atmospheric effects. The encapsulation system must be chemically stable, able to withstand high temperatures, and impermeable to fulfill its function as a barrier layer.

[0112] The stack can be covered by a packaging system, the packaging system comprising:

[0113] - An optional first dense insulating capping layer, preferably selected from parylene, parylene F, polyimide, epoxy resin, acrylate, fluoropolymer, silicone resin, polyamide, sol-gel silica, organosilicon and / or mixtures thereof, is deposited on the stack of anode and cathode foils; and

[0114] - An optional second capping layer, composed of an electrically insulating material, is deposited on the stack of anode and cathode foils or on the first capping layer by atomic layer deposition; and

[0115] - Based on a key characteristic, at least a third impermeable covering layer, preferably with a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 .d, the third capping layer is made of ceramic material and / or low-melting-point glass, preferably glass with a melting point below 600°C, and is deposited on the stack of anode and cathode foils or around the first capping layer.

[0116] It should be understood that the sequence of the at least one second capping layer and the at least one third capping layer can be repeated z times, where z≥1, and deposited on the periphery of at least the third capping layer. The last layer of the encapsulation system is an impermeable capping layer, preferably with a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 .d, made of ceramic materials and / or low-melting-point glass.

[0117] This sequence can be repeated z times, where z ≥ 1. It has a blocking effect, which increases with the value of z.

[0118] Water vapor transmission rate can be determined using the method described in U.S. Patent No. 7,624,621 and the published literature by A. Mortier et al. in Thin Solid Films 6+550 (2014) 85-89. Structural properties of ultraviolet cured polysilazane gas barrier layers on polymer substrates" The method described in the document is used for determination.

[0119] Typically, the first capping layer is optional and selected from: silicone resins (e.g., deposited from hexamethyldisiloxane (HMDSO) by impregnation or plasma-enhanced chemical vapor deposition), epoxy resins, polyimides, polyamides, parylene (also known as poly(p-xylene), but more commonly referred to as parylene), and / or mixtures thereof. When the first capping layer is deposited, it protects the sensitive components of the battery from their environmental influences. The thickness of the first capping layer is preferably between 0.5 μm and 3 μm.

[0120] This first capping layer is particularly useful when the electrolyte and electrode layers of a battery have pores: it acts as a planarization layer and also has a barrier effect. For example, this first layer can be lining the surface of micropores that have openings on the surface of the layer, sealing their entrances.

[0121] Different parylene variants can be used in this first capping layer. Parylene C, parylene D, parylene N (CAS 1633-22-3), parylene F, or mixtures of parylene C, D, N, and / or F can be used. Parylene is a dielectric, transparent, semi-crystalline material with high thermodynamic stability, excellent solvent resistance, and extremely low permeability. Parylene also has barrier properties. Parylene F is preferred within the scope of this invention.

[0122] The first capping layer is preferably obtained by condensing gaseous cells deposited on the surface of the battery stack via chemical vapor deposition (CVD), which achieves conformal, thin, and uniform coverage of all accessible surfaces of the stack. The first capping layer is preferably rigid; it cannot be considered a flexible surface.

[0123] The second capping layer is also optional and is formed of an electrically insulating material, preferably an inorganic material. It is deposited via atomic layer deposition (ALD), PECVD, HDPCVD (high-density plasma chemical vapor deposition), or ICP CVD (inductively coupled plasma chemical vapor deposition) to achieve conformal coverage of all accessible surfaces of the stack previously covering the first capping layer. ALD deposited layers are mechanically very fragile and require a hard surface to function properly. Depositing a fragile layer on a flexible surface can lead to crack formation, resulting in a loss of integrity in the protective layer. Furthermore, the growth of the ALD deposited layer is affected by the substrate properties. Layers deposited by ALD on substrates with different chemical properties will grow unevenly, leading to a loss of integrity in the protective layer. Therefore, this optional second layer (if present) is preferably attached to the optional first layer, ensuring a chemically uniform substrate growth.

[0124] ALD deposition techniques are particularly suitable for covering high-roughness surfaces in a completely impermeable and conformal manner. They can produce conformal layers, free of defects such as pores (so-called "pinhole-free" layers), and have very good barrier properties. Their water vapor transmission rate (WVTR) is extremely low. WVTR is used to evaluate the water vapor permeability of the encapsulation system. The lower the WVTR, the more impermeable the encapsulation system. The thickness of the second layer is preferably selected based on the desired level of impermeability (i.e., the desired WVTR) and depends on the deposition technique used, particularly those selected from ALD, PECVD, HDPCVD, and ICP CVD.

[0125] The second capping layer can be made of ceramic, vitreous, or glass-ceramic materials, such as oxides, nitrides, phosphates, oxynitrides, or siloxanes of the Al2O3 or Ta2O5 type. The thickness of the second capping layer is preferably between 10 nm and 10 µm, more preferably between 10 nm and 50 nm.

[0126] The second capping layer, deposited on top of the first capping layer via ALD, PECVD, HDPCVD (high-density plasma chemical vapor deposition), or ICP CVD (inductively coupled plasma chemical vapor deposition), firstly makes the structure impermeable, preventing water migration into the interior of the object, and secondly protects the first capping layer, preferably made of parylene F, from the atmosphere, especially air and water, and from the effects of heat exposure to prevent its degradation. Therefore, the second capping layer improves the lifespan of the encapsulated battery.

[0127] The second capping layer can also be deposited directly on the stack of anode and cathode foils, i.e., without depositing the first capping layer.

[0128] The third capping layer must be impermeable, which means its water vapor transmission rate (WVTR) is preferably less than 10. -5 g / m 2 .d. The third capping layer is formed by depositing a ceramic material and / or a low-melting-point glass, preferably a glass with a melting point below 600°C, around the periphery of the anode and cathode foil stack or around the first capping layer. The ceramic and / or glass material used in this third layer is preferably selected from:

[0129] - Low melting point glass (typically >600℃), preferably SiO2-B2O3; Bi2O3-B2O3, ZnO-Bi2O3-B2O3, TeO2-V2O5, PbO-SiO2,

[0130] - Oxides, nitrides, nitrogen oxides, Si x N y SiO2, SiON, amorphous silicon or SiC.

[0131] These glasses can be deposited through molding or dip coating.

[0132] Ceramic materials are preferably deposited at low temperatures via PECVD or, more preferably, HDPCVD or ICP CVD; these methods can deposit layers with good impermeability.

[0133] The coated stack is then cut along the D'n and Dn cutting lines by any suitable means to expose the anode and cathode connection regions and obtain a cell.

[0134] Contact elements (electrical contacts) are added where the cathode connection area or the corresponding anode connection area is clearly visible. These contact areas are preferably located on opposite sides of the battery stack for collecting current (lateral current collectors). The contact elements are arranged at least on the cathode connection area and at least on the anode connection area, preferably on a coated and cut stack surface that includes at least the cathode connection area and on a coated and cut stack surface that includes at least the anode connection area.

[0135] The preferred contact element is composed of stacked layers near the cathode connection region and the anode connection region. The stack includes a first electrical connection layer and a second layer consisting of a metal foil disposed on the first layer. The first electrical connection layer includes a material filled with conductive particles, preferably a polymer resin filled with conductive particles and / or a material obtained by the sol-gel method, more preferably a polymer resin filled with graphite.

[0136] When the circuit is subjected to thermal stress and / or vibration stress, the first electrical connection layer secures the subsequent second electrical connection layer while providing "flexibility" at the connection without disrupting the electrical contact.

[0137] The second electrical connection layer is preferably a metal foil. This second electrical connection layer provides durable waterproof protection for the battery. Generally, for a given material thickness, metals can be used to create highly impermeable films, more impermeable than ceramic films, and even more impermeable than polymer films, which are typically not very impermeable to water molecules. This extends the battery's calendar life by reducing the water-to-vitality ratio (WVTR) at the contact elements.

[0138] Typically, each first layer is bonded to either the anode or cathode terminal separately using an adhesive. With this in mind, conductive adhesive layers can be used. In particular, two layers of conductive adhesive with different properties can be used. These layers are "sequential," meaning the first layer covers the terminal, and the second layer covers the first layer. Preferably, the two conductive adhesives can have different physicochemical properties, particularly different wetting properties.

[0139] Typically, the aforementioned metal foil is also bonded to the first layer using an adhesive, more precisely, a conductive adhesive, which preferably must be electrochemically stable when in contact with the electrode. This use of a conductive adhesive to bond the metal foil improves the impermeability of the terminal and reduces its resistance. Regardless of the method of manufacturing this foil, this technical effect is noteworthy.

[0140] Preferably, a third electrical connection layer comprising conductive ink is deposited on the second electrical connection layer; the purpose is to reduce WVTR, thereby extending the battery's lifespan.

[0141] The contact elements allow for alternating electrical connections between the positive and negative terminals at each end. These contact elements enable parallel electrical connections between different battery cells. For this purpose, only the cathode connection protrudes at one end, while the anode connection is available at the other end.

[0142] Now will describe Figures 1 to 3 To illustrate the invention, these figures schematically show multilayer batteries encapsulated according to different embodiments of the invention. They correspond to cross-sections perpendicular to the layer thickness.

[0143] Use an orthogonal coordinate system XYZ, where...

[0144] - Axis XX is the first horizontal axis, meaning it is contained within the planes of the different layers that make up the stack. Furthermore, axis XX is referred to as transverse, meaning it extends laterally relative to the foil. In particular, it is perpendicular to the plane of the contact element, which will be described below.

[0145] - Axis YY is a second horizontal axis, also contained within the planes that make up the different layers of the stack. Axis YY is called sagittal, meaning it extends from the back to the front of the foil. In particular, it is parallel to the plane of the contact element.

[0146] Finally, axis ZZ extends vertically, perpendicular to each of the axes mentioned above. It is also known as the front axis.

[0147] Figure 1 A battery I according to a first embodiment of the present invention is shown. The battery includes a single cell 1. More specifically, the cell 1 is formed of an anode layer 2, an electrolyte layer 3, and a cathode layer 2'. The encapsulation system 4 includes three distinct layers, one on top of the other: a first layer 11 as explained above, then a second cover layer 12 as explained above, and finally a third cover layer 13 as explained above.

[0148] Here, the encapsulation system covers four of the six sides of the battery (if it is represented by a cuboid). Each of the two sides not covered by the encapsulation system, preferably laterally opposite each other, defines at least one electrical connection region; the first side not covered by the encapsulation system defines the anode connection region, and the second side not covered by the encapsulation system defines the cathode connection region to prevent any short-circuit risk.

[0149] The battery also includes contact elements, which are generally indicated by the corresponding reference numerals 8 and 8'. As described above, each contact element includes a first electrical connection layer 5 or 5' and a second electrical connection layer 6 or 6'.

[0150] Figure 2 A battery II according to a second embodiment of the present invention is shown. This battery II comprises a stack consisting of four cell units 1a, 1b, 1c, and 1d. (See reference...) Figure 1 As explained, the packaging system 4 comprises three distinct layers. Contact elements 8 and 8' are referenced above. Figure 1 The contact elements described are similar.

[0151] Figure 3 Battery III according to a third embodiment of the present invention is shown. As referenced... Figure 2 The battery comprises a stack of four cell units. The packaging system 4 comprises three consecutive layers of two distinct layers: a second cover layer 12 as explained above and a third cover layer 13 as explained above. Finally, contact elements 8 and 8' are referenced above. Figure 1 The contact elements described are similar.

[0152] It should be noted that, Figures 1 to 3 Battery I, II, and III must meet the impermeability requirement, which is a key criterion of this invention. Therefore, contact elements 8 and 8' are manufactured using conductive materials that meet this impermeability criterion. Such materials are, for example, conductive glass, particularly those filled with metal powder (e.g., chromium particles, aluminum particles, copper particles, and other electrochemically stable metal particles (preferably nanoparticles) at the electrode operating voltage).

[0153] As is known per se, multiple cell stacks, such as those described above, can be produced simultaneously. This improves the efficiency of the overall battery manufacturing method of the present invention. In particular, large-size stacks formed by alternating cathode layers and corresponding anode layers or foils can be produced.

[0154] The physicochemical structure of each anode foil or cathode foil, such as that known in the French patent document FR3091036 filed by the applicant, is not within the scope of this invention and will only be described briefly. Each anode foil or corresponding cathode foil includes an anode active layer or a corresponding cathode active layer. Each of these active layers can be solid, i.e., they have dense or porous properties. Furthermore, to prevent electrical contact between two adjacent foils, an electrolyte layer or a liquid electrolyte-impregnated insulating layer is provided on at least one of the two foils to contact the opposing foil. The electrolyte layer or liquid electrolyte-impregnated insulating layer (not shown in the figures describing the invention) is sandwiched between two foils of opposite polarity, i.e., between the anode foil and the cathode foil.

[0155] These layers are notched to define so-called empty areas, allowing for the separation of different final cells. Within the scope of this invention, different shapes can be specified for these empty areas. As the applicant has already proposed in French patent document FR 3091036, these empty areas can be H-shaped. Appendix Figure 4A The figure shows a stack 1100 between an anode foil or layer 1101 and a cathode foil or layer 1102. As shown in the figure, cuts are formed in these different foils to create the H-shaped anode void 1103 and the corresponding cathode void 1104.

[0156] Alternatively, these free zones can also be I-shaped. (Appendix) Figure 4B The stack 1200 between the anode foil or layer 1201 and the cathode foil or layer 1202 is shown. Figure 4B As shown, cuts are formed in these different foils to create the I-shaped anode void 1203 and the corresponding cathode void 1204.

[0157] Preferably, once the fabrication of the different cell stacks is complete, each anode and each cathode of a given battery includes a respective first body separated from a respective second body by a space devoid of any electrode material, electrolyte, and / or conductive substrate. According to other alternative embodiments not shown, cavities of shapes other than H-shaped or I-shaped can be provided, such as U-shaped cavities. Nevertheless, H-shaped or I-shaped cavities are preferred. During the manufacturing process, the cavities can be filled with resin.

[0158] Figure 5Other preferred alternative embodiments are illustrated in the following figures, in which the battery further includes a support member. These figures schematically show the stack 1, the front packaging regions 40 and 41, and the contact elements 8 and 8'. The support member 50 is typically flat and generally less than 300 μm thick, preferably less than 100 μm. The support member is preferably made of a conductive material, typically a metallic material, particularly aluminum, copper, or stainless steel, which may be coated with thin layers of gold, nickel, and tin to improve its solderability. The front side of the support member is indicated by reference numeral 51 and faces the stack 9, while the opposite back side is indicated by reference numeral 52.

[0159] The support member has holes, specifically spaces 53 and 54, defining a central base plate 55 and two opposing crossbars 56 and 57. The different regions 55, 56, and 57 of the support member are therefore electrically insulated from each other. Specifically, as will be seen below, crossbars 56 and 57 form areas that are electrically insulated from each other and can be connected to contact elements belonging to the battery. In the illustrated example, electrical insulation is achieved by providing empty spaces 53 and 54, which, as will be seen below, are filled with reinforcing material. Alternatively, these spaces could be filled with non-conductive materials such as polymers, ceramics, or glass.

[0160] In the example shown, the support and the stack are connected to each other via layer 60. The latter is typically formed with a non-conductive adhesive, particularly an epoxy or acrylate type adhesive. Alternatively, the support and the stack can be rigidly fixed to each other by welding (not shown). For example, the thickness of layer 60 is between 5 µm and 100 µm, particularly approximately 50 µm. Depending on the main plane of the support 50, this layer at least partially covers the aforementioned spaces 53 and 54 to insulate the anode and cathode contact elements from each other, as described in detail below. Furthermore, conductive adhesive pads 30 and 31 allow the contact elements to be secured to the support 50 while ensuring electrical continuity.

[0161] According to the first possibility, corresponding to Figure 5 In the illustrated embodiment, the material forming contact elements 8 and 8' achieves an impermeable seal function that meets the aforementioned criteria. For this purpose, such material typically belongs to the category listed above with reference to the first three figures. In this case, no additional encapsulation is required. More specifically, due to the presence of the impermeable contact elements and encapsulation, the unit stack of the anode and cathode prevents the penetration of potentially harmful gases.

[0162] According to the second possibility, corresponding to Figure 6 In the illustrated embodiment, the material forming contact elements 8 and 8' is not impermeable as understood within the scope of this invention. In this case, the battery preferably includes other so-called encapsulation layers 45, such as... Figure 6The solid lines in the diagram indicate this. The other encapsulation layers provide the necessary impermeability for the stack, and are therefore "re-encapsulated." Preferably, the material of layer 45 has the same definition as the last layer of the encapsulation system. Therefore, the water vapor transmission rate (WVTR) of layer 45 is preferably less than 10. -5 g / m 2 .d, and the layer 45 is made of ceramic material and / or low-melting-point glass. In this embodiment, the "impermeable cover" layer is thus formed by the last layer of the initial encapsulation system constituting the so-called first impermeable cover layer and other layers 45 constituting the so-called other impermeable cover layers.

[0163] To ensure the critical criterion of impermeability, the additional encapsulation layer 45 first covers the contact elements 8 and 8'. Furthermore, it extends into the intermediate space formed between the initial encapsulation layer 41 and the opposing surfaces of the support 50. Finally, it also extends into the free spaces 53 and 54 within the support. Figure 6 At the bottom, reference numeral 45 appears more than three times, indicating these specific areas. Therefore, components harmful to the normal operation of the battery cannot enter the cell stack of the anode and cathode. In other words, this invention prevents any possible "entry" of these harmful components.

[0164] According to a third possibility (not shown), the cell stack is first placed solely on the support, with a non-conductive adhesive layer inserted. Then, contact elements are used to cover the sides of the stack. Considering this, cell stacks already equipped with these contact elements but without their encapsulation system can also be placed on their support. Finally, as described above, the encapsulation system is deposited, taking care to ensure complete impermeability.

[0165] Finally, according to a preferred embodiment of the invention, the battery can be further equipped with a reinforcement system. This can be initially applied to, for example... Figure 5 The battery shown has impermeable contact elements. Therefore, this reinforcement system as a whole is indicated by reference numeral 80. In this case, the reinforcing material covers the top surface of the battery and the lateral contact elements. This reinforcing material also preferably fills the intermediate space between the layer 41 and the support 50, as well as the free spaces 53, 54 in the support. To illustrate this filling, reference numeral 80 is used repeatedly to indicate the different areas occupied by the reinforcing material.

[0166] In the manner not shown, reinforcing materials can also be applied. Figure 6 The battery has non-impermeable contact elements. In this case, reinforcing material covers the top and lateral edges of the other encapsulation system 45. It should be noted that this reinforcing material can be tightly bonded to the encapsulation material 45 in the free spaces 53, 54 and in the intermediate space between layer 41 and support 50.

[0167] The reinforcing system 80 can be made of any material that provides this mechanical stiffness. With this in mind, for example, a resin consisting of a polymer only or a polymer filled with inorganic fillers can be selected. The polymer matrix can be derived from, for example, families of epoxy resins, acrylates, or fluoropolymers, and the fillers can be formed from particles, flakes, or glass fibers.

[0168] Preferably, the strengthening system 80 can provide additional waterproofing. With this in mind, a low-melting-point glass can be selected, for example, to ensure mechanical strength and provide additional waterproofing. The glass can be, for example, derived from the SiO2-B2O3; Bi2O3-B2O3, ZnO-Bi2O3-B2O3, TeO2-V2O5, or PbO-SiO2 family.

[0169] Typically, the reinforcement system 80 is much thicker than the packaging system. (Reference) Figure 5 The minimum thickness of this reinforcement system at the front cover of the stack is indicated by the reference numeral E80. The preferred thickness E80 is between 20 µm and 250 µm, typically equal to approximately 100 µm. The presence of the additional reinforcement system provides additional advantages. This reinforcement system thus provides mechanical and chemical protection, optionally combined with additional gas barrier functions.

[0170] As described above, integrating the battery of the present invention onto the support 50 can be achieved by stacking each cell individually on its support. Nevertheless, it is preferable to manufacture multiple batteries simultaneously, each integrated with the support.

[0171] Taking this into account, this simultaneous manufacturing method, such as Figures 7 to 9 As shown. To implement this method, a support frame 105 designed to form multiple support members 50 is preferably used. Figure 7 The frame 104, shown at a large scale, has an outer boundary 150 and multiple preforms 151, each preform allowing the fabrication of a corresponding battery. In the example shown, twelve identical preforms are arranged in three rows and four columns. Alternatively, frames with different numbers of such preforms can be used.

[0172] Each prefabricated component includes a central region 155 for forming a base plate 55, and two side blocks 156 and 157 for forming crossbars 56 and 57, respectively. The region and blocks are separated from each other by slots 153 and 154, which are designed to form spaces 53 and 54. The different prefabricated components are secured to each other and to their outer edges by different horizontal bars 158 and vertical bars 159.

[0173] In this embodiment, each preform 151 receives a pre-encapsulated battery, which is consistent with... Figure 1Consistent with the above. In terms of manufacturing method, a certain amount of non-conductive adhesive 106 is deposited on each region 155 to form layer 6, and a certain amount of conductive adhesive 130 and 131 is deposited to form pads 30 and 31. The encapsulated stack is then placed in contact with the support, thereby forming adhesive layer 60 and pads 30 and 31, thereby allowing the stack to be secured to the support.

[0174] Finally, as Figure 9 As shown, cutouts are formed in frame 150, on which different components of multiple batteries are mounted. Different cut lines are marked with dashed lines, and cuts in the longitudinal dimension of the battery are indicated by reference numeral D, while cuts in its transverse dimension are indicated by reference numeral D'. It should be noted that certain areas R and R' are omitted in both dimensions of the frame.

[0175] According to an alternative embodiment not shown, the electrochemical device of the present invention may include one or more other electronic components. For example, such a component may be of the LDO (“low dropout regulator”) type. Typically, it is conceivable to manufacture miniature circuits with complex electronic functions. With this in mind, an RTC (“real-time clock”) module or an energy harvesting module may be used. In this embodiment, one or more electronic components are preferably covered by the same packaging system as the packaging system of the protection unit stack.

[0176] In operation, electrical energy is stored in the unit stack in a conventional manner. This energy is transferred via contact elements and conductive adhesive pads 30 and 31 to conductive areas 55 and 56 of the support 50. Since these conductive areas are insulated from each other, there is no risk of short circuits. The electrical energy is then diverted from areas 56 and 57 to any suitable type of energy-consuming device.

[0177] exist Figure 10 The energy-consuming device is shown graphically and is designated by reference numeral 1000. It includes a body 1002, on which the lower surface of a support rests. The mutual fastening between the body 1002 and the support 50 is achieved by any suitable means. It should be noted that... Figure 10 In the middle, device 1000 integrates Figure 5 The battery shown has impermeable contact elements. According to an alternative embodiment not shown, Figure 6 The battery in this case can also be combined with the energy consumption device 1000. In this case, as mentioned above, it is necessary to ensure that the other encapsulation material 45 makes the cell stack of the anode and cathode completely impermeable. Refer to the above description in this regard, especially regarding Figure 6 The different positions of the reference numeral 45 in the attached figure.

[0178] The device 1000 also includes an energy-consuming element 1004 and connecting lines 1006 and 1007 electrically connecting regions 56 and 57 of the support 50 to the element 1004. Its control can be provided by components of the battery itself and / or by components belonging to the device 1000 (not shown). As a non-limiting example, the energy-consuming device may be an amplifier-type electronic circuit, a clock-type electronic circuit (e.g., a real-time clock (RTC) component), a volatile memory-type electronic circuit, a static random access memory (SRAM)-type electronic circuit, a microprocessor-type electronic circuit, a watchdog timer-type electronic circuit, a liquid crystal display component, an LED (light-emitting diode)-type component, a voltage regulator-type electronic circuit (e.g., a low-dropout regulator (LDO) circuit), or a CPU (central processing unit)-type electronic component.

[0179] Now refer to Figure 11 and Figure 12 To describe an alternative embodiment, the conductive support 750 is of a multi-layered type, in contrast to the single-layered type of the aforementioned support 50. Furthermore, this support 750 is of a solid type, specifically in contrast to the perforated type of metal mesh described above. Figure 11 As shown, the support 750 is formed of multiple layers, such as those made of a polymer material. These layers extend one beneath another, with their main planes substantially parallel to the planes forming the layers stacked as described above. Therefore, the structure of this support is similar to that of a printed circuit board (PCB).

[0180] Figure 11 and Figure 12 The layer 756, on which the battery stack will be deposited, is shown from top to bottom. Layer 756 is primarily made of a polymeric material such as epoxy resin and has two inserts 757. The inserts 757 are made of a conductive material, particularly a metallic material, and are designed to mate with the anode and cathode contacts of the battery. It should be noted that these inserts 757 are insulated from each other due to the epoxy resin of layer 756.

[0181] Directly below layer 756 is layer 758, also formed of a polymer material such as epoxy resin. Layer 758 is equipped with two inserts 759 made of conductive material, which are in electrical contact with the first insert 757. Like layer 756, these inserts 759 are insulated from each other.

[0182] Then there is an intermediate layer 760, which is significantly different from layers 756 and 758 described above. More specifically, layer 760 is formed of a conductive material generally similar to that used to form the inserts 757 and 759 described above. This layer is equipped with two annular inserts 761 made of an insulating material, particularly epoxy resin as described above. These inserts 761 receive a disk 762 made of a conductive material in their hollow central portion, and the disk 762 contacts the adjacent conductive insert 759. It should be noted that these conductive disks 762 are insulated from each other by the rings 761.

[0183] Finally, existence Figure 11 and Figure 12 The bottom layers 764 and 766 are identical to the layers 758 and 756 described above, respectively. Layer 764 is equipped with two inserts 765 that contact the disk 762, while the bottom layer 766 is equipped with two inserts 767 that contact the aforementioned inserts 765. The different conductive inserts 757, 759, 762, 765, and 767 define conductive paths indicated by reference numerals 753 and 754, which are electrically connected to the opposite end faces of the support 705. These conductive paths are insulated from each other through layers 756, 758, 764, and 766 or through the disk 761.

[0184] In this embodiment, the reinforcement system may differ from the reinforcement system 80 of the first embodiment. The protective film 780 can be deposited, in particular, via a lamination step. This barrier film, for example, is made of polyethylene terephthalate (PET) incorporating inorganic multilayers; suitable products for this application could be Ultra Barrier Film 510 or Ultra Barrier Solar Films 510-F purchased from 3M. However, this reinforcement system using rolled films, in addition to… Figure 11 In addition to the applications shown, it can also be used for other applications.

[0185] Figure 11 Further illustration shows the integration of a support 705, a stack 702, conductive pads 730 and 740, an encapsulation 707, and a thin film 708 onto the energy-consuming device 1000. Similar to the first embodiment, the energy generated at the stack 702 is transferred to the upper insert 757 via contact elements 730 and 740. This energy is then transferred to the energy-consuming device 1000 along the connection paths 753 and 754 described above.

[0186] In its most common structure, a multi-layered support can be formed by just two separate layers, one beneath the other. These layers define conductive paths, similar to conductive paths 753 and 754 described above. (Reference) Figure 11The particular embodiment shown has specific advantages. More specifically, for example, the thickness of the multilayer support, indicated by reference numeral 750, is very small, preferably less than 100 μm. This support further benefits from particularly satisfactory flexural strength when integrated into flexible electronic circuits.

[0187] This invention is not limited to the examples described and illustrated.

[0188] According to a first alternative embodiment not shown, each current collector substrate may be perforated, i.e., it may have at least one through-hole. Preferably, the lateral dimension of each hole (or opening) is between 0.02 mm and 1 mm. Furthermore, the porosity of each perforated substrate is between 10% and 30%. This means that for a given surface area of ​​the substrate, 10% to 30% of that surface area is occupied by holes.

[0189] The technical purpose of these holes or openings is as follows: the first layer deposited on one of the two surfaces of the substrate will bond with the first layer deposited on the other surface within the opening. This improves the quality of the deposition, particularly the adhesion of the layer in contact with the substrate. More specifically, during the drying and sintering operations, the aforementioned layers undergo slight shrinkage, i.e., their longitudinal and transverse dimensions decrease slightly, while the dimensions of the substrate remain essentially unchanged. This often generates shear stress at the interface between the substrate and each layer, thereby reducing adhesion quality; this stress increases with increasing layer thickness.

[0190] Under these conditions, providing a porous substrate significantly improves the quality of this adhesion. Essentially, layers on opposite surfaces of the substrate tend to bond together within different pores. This allows for increased layer deposition thickness, even if they no longer contain organic binders after annealing. This alternative embodiment also allows for increased battery power. It is particularly suitable for use with ultra-high power electrodes of the thick mesopore type.

[0191] The method of the present invention is particularly suitable for manufacturing solid-state batteries, i.e., batteries whose electrodes and electrolytes are solid and do not include a liquid phase, or are even immersed in a solid phase.

[0192] The method of the present invention is particularly suitable for manufacturing quasi-solid-state batteries comprising at least one separator layer impregnated with an electrolyte.

[0193] The isolation layer is preferably a porous inorganic layer, which has the following characteristics:

[0194] - Porosity, preferably mesoporous, greater than 30%, preferably between 35% and 50%, more preferably between 40% and 50%.

[0195] - Average diameter D of the hole 50 Less than 50 nm.

[0196] The separator is generally understood to be sandwiched between electrodes. In this exemplary embodiment, it is a ceramic or glass-ceramic filter deposited on at least one electrode and sintered to form a solid component of the battery. The fact that the liquid is nanocompressed within the separator gives the final battery quasi-solid-state characteristics.

[0197] The thickness of the separator layer is preferably less than 10 μm, more preferably between 3 μm and 16 μm, more preferably between 3 μm and 6 μm, and even more preferably between 2.5 μm and 4.5 μm, thereby reducing the final thickness of the battery without compromising its characteristics. The pores of the separator layer are filled with an electrolyte, preferably a lithium-ion carrying phase, such as a liquid electrolyte containing lithium salts or an ionic liquid. The liquid, "nano-confined" or "nano-trapped," cannot escape from the pores, especially the mesopores. It is bound by a phenomenon known here as "mesopore structure absorption" (which does not appear to be described in the literature related to lithium-ion batteries), and cannot escape even when the battery is placed in a vacuum. This type of battery is therefore considered a quasi-solid-state battery.

[0198] The method and packaging system described in this invention can be applied to any type of thin-film battery, especially any type of lithium-ion battery.

[0199] These lithium-ion batteries can be solid-state multilayer lithium-ion batteries, quasi-solid-state multilayer lithium-ion batteries, and especially solid-state multilayer lithium-ion micro-batteries. More generally, these lithium-ion batteries can specifically use an anode layer, an electrolyte layer, and a cathode layer, such as those described in international patent document WO 2013 / 064777 in the field of micro-batteries, namely the anode layer made of one or more materials as described in claim 13, the cathode layer made of one or more materials as described in claim 14, and the electrolyte layer made of one or more materials as described in claim 15.

[0200] The battery described in this invention can be a lithium-ion microcell, a lithium-ion mini-cell, or a high-power lithium-ion battery. In particular, the battery can be designed and sized to have a capacity of less than or equal to about 1 mA h (commonly referred to as a "microcell"), a power greater than about 1 mA h to about 1 Ah (commonly referred to as a "mini-cell"), or a capacity greater than about 1 Ah (commonly referred to as a "high-power battery"). Typically, microcells are designed to be compatible with methods of manufacturing microelectronic products.

[0201] We can produce every type of battery in these three power ranges:

[0202] - A layer of "solid" type, i.e., a liquid or paste phase without impregnation (the liquid or paste phase may be a lithium-ion conductive medium capable of acting as an electrolyte).

[0203] - Or a layer of mesoporous "solid" type, impregnated typically with a liquid or paste phase of a lithium-ion conductive medium, which spontaneously permeates through the layer and no longer emerges from it; therefore, this layer can be considered quasi-solid.

[0204] - Or have impregnated porous layers (i.e., layers with open-cell networks, which can be impregnated with liquid or paste phases to give these layers wet properties).

Claims

1. Battery, including: - At least one cell unit, the cell unit comprising, in sequence, an anode current collector substrate, an anode layer, an electrolyte material layer or an electrolyte-impregnated separator layer, a cathode layer, and a cathode current collector substrate. In the case where the battery comprises multiple cell units, the second cell unit is placed on top of the first cell unit in the order shown in the layers, and so on. - A packaging system that covers the periphery of the cell unit, or, in the presence of multiple cell units, covers at least a portion of the periphery of all cell units. - At least one anode contact element designed to form an electrical contact between the at least one cell and an external conductive element, the cell including a first contact surface defining at least one anode connection region, and - At least one cathode contact element designed for electrical contact with an external conductive element, the battery including a second contact surface defining at least one cathode connection region. The battery is characterized in that the packaging system comprises at least the following sequence: - The coating, composed of electrically insulating materials, is deposited using atomic layer deposition. - Impermeable layer with a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 d, the impermeable layer is made of ceramic material and / or low-melting-point glass with a melting point below 600°C, and the impermeable layer is deposited on the coating. The sequence of coating and impermeable layer is repeated z times, where z≥1, and the last layer of the encapsulation system is an impermeable layer consisting of the sequence of coating and impermeable layer.

2. The battery according to claim 1, characterized in that, The thickness of the impermeable layer is between 1 μm and 50 μm.

3. The battery according to claim 2, characterized in that, The thickness of the impermeable layer is between 1 μm and 10 μm.

4. The battery according to claim 1, characterized in that, The encapsulation system also includes a capping layer selected from parylene, parylene F, polyimide, epoxy resin, silicone resin, polyamide, sol-gel silica, organosilicon and / or mixtures thereof, covering the periphery of the cell or, in the presence of multiple cells, covering at least a portion of the periphery of all cells, wherein a sequence of coatings and impermeable layers is deposited repeatedly z times on the capping layer.

5. The battery according to claim 1, characterized in that, The sequence of coatings and impermeable layers, repeated z times, is deposited directly on the periphery of the cell or, in the presence of multiple cells, covers at least a portion of the periphery of all cells.

6. The battery according to claim 1, characterized in that, Each of the anode contact element and the cathode contact element includes: - A first electrical connection layer disposed on at least an anode connection region and at least a cathode connection region, the first electrical connection layer comprising a material filled with conductive particles. - A second electrical connection layer, comprising a metal foil disposed on a first material layer filled with conductive particles.

7. The battery according to claim 6, wherein the metal foil is of the self-supporting type.

8. The battery according to claim 6, wherein the metal foil is prepared by rolling or electroplating.

9. The battery according to claim 7, characterized in that, The metal foil has a thickness between 5 and 200 micrometers and is made of one of the following materials: nickel, stainless steel, copper, molybdenum, tungsten, vanadium, tantalum, titanium, aluminum, chromium, and alloys containing them.

10. The battery according to claim 6, characterized in that, Each of the anode contact element and the cathode contact element includes a third layer, which includes conductive ink disposed on the second electrical connection layer.

11. The battery according to claim 1, further comprising: - An electrical connection support, at least partially made of a conductive material, disposed near the end face of the cell. - An electrical insulation device that insulates two distant regions of the connecting support from each other, these distant regions forming their respective electrical connection paths. - The anode contact element enables a first side of each cell to be electrically connected to a first electrical connection path, while the cathode contact element enables a second side of each cell to be electrically connected to a second electrical connection path.

12. The battery of claim 11, wherein the electrical connection support is of a single-layer type.

13. The battery of claim 11, wherein the electrical connection support comprises a plurality of layers, wherein one layer is disposed below another layer.

14. The battery of claim 11, wherein the last layer of the encapsulation system comprises a first layer that does not respectively cover the anode contact element and the cathode contact element, and other layers that cover all or part of the contact elements and at least partially cover the electrical connection support.

15. The battery according to claim 1, characterized in that, It is a lithium-ion battery.

16. The battery according to claim 1, characterized in that, It is a solid-state lithium-ion battery.

17. The battery according to claim 1, characterized in that, It was designed and sized to have a capacity of less than or equal to 1 mA h.

18. The battery according to claim 1, characterized in that, It was designed and sized to have a capacity greater than 1 mA h.

19. A method for manufacturing a battery according to any one of the preceding claims, the method comprising: a) Provide at least one anode current collector substrate foil, the anode current collector substrate foil being coated with an anode layer. b) Provide at least one cathode current collector substrate foil, the cathode current collector substrate foil being coated with a cathode layer. At least one of the anode current collector substrate foil coated with an anode layer or the cathode current collector substrate foil coated with a cathode layer includes an electrolyte material layer or an electrolyte-impregnated insulating layer. c) Prepare an alternating stack (I) of at least one anode current collector substrate foil coated with an anode layer and at least one cathode current collector substrate foil coated with a cathode layer to sequentially obtain at least one anode current collector substrate, at least one anode layer, at least one electrolyte material layer or an electrolyte-impregnated isolation layer, at least one cathode layer and at least one cathode current collector substrate. d) The alternating foil stacks obtained in step c) of heat treatment and / or mechanical compression form a stable stack. e) To form a packaged system, the step of encapsulating the robust stack is performed by depositing at least the following sequence around the periphery of the battery: - The coating, composed of electrically insulating materials, is deposited using atomic layer deposition (ALD). - Impermeable layer with a water vapor transmission rate (WVTR) of less than 10. -5 g / m 2 ·d, the impermeable layer is made of ceramic material and / or low-melting-point glass with a melting point below 600°C, and is deposited on the coating. The sequence of coating and impermeable layer is repeated z times, where z≥1, and the last layer of the encapsulation system is an impermeable layer consisting of the sequence of coating and impermeable layer. f) Create two cuts (Dn, D'n) to form a cut stack that exposes at least the anode connection region and the cathode connection region; g) Prepare anode contact elements and cathode contact elements.

20. The method of claim 19, wherein step e) further comprises depositing at least one capping layer, selected from parylene, parylene F, polyimide, epoxy resin, silicone resin, polyamide, sol-gel silica, organosilica and / or mixtures thereof, on a stable stack, and repeating the sequence of coatings and impermeable layers on said capping layer.

21. The method of claim 19, wherein the sequence of coatings and impermeable layers repeated z times is directly deposited on a stable stack.

22. The method of claim 19, wherein the fabrication of the anode contact element and the cathode contact element comprises: - Deposit a first electrical connection layer made of a material filled with conductive particles on at least the anode connection region and at least the cathode connection region. - A second electrical connection layer is deposited on the first electrical connection layer, wherein the second electrical connection layer is a metal foil or a metal ink.

23. The method of claim 22, wherein the metal foil is formed by rolling and then the metal foil thus formed is applied to the first electrical connection layer.

24. The method of claim 22, wherein the metal foil is formed directly by electroplating in situ or off-site relative to the first metal bonding layer.

25. The method of claim 19, wherein after step g), the method includes step h) depositing conductive ink on at least the anode connection region and the cathode connection region of the battery coated with the first and second electrical connection layers.

26. The method according to claim 19, characterized in that... The low-melting-point glass is selected from SiO2-B2O3, Bi2O3-B2O3, ZnO-Bi2O3-B2O3, TeO2-V2O5 and PbO-SiO2.

27. The method according to claim 19, characterized in that, The coating and at least one sequence of impermeable layers are deposited by PECVD.

28. The method according to claim 19, characterized in that, The coating and the impermeable layer, at least one sequence of coatings, include oxides and / or nitrides and / or Ta2O5 and / or oxynitrides and / or Si. x N y And / or SiO2 and / or SiON and / or amorphous silicon and / or SiC.

29. The method according to claim 19, wherein, After placing the electrical connection support near the end face of the cell stack, the packaging system is formed.

30. The method according to claim 19, wherein, The packaging system is formed before the electrical connection support is placed near the end face of the cell stack.

31. The method of claim 19, wherein the first layer of the last layer of the encapsulation system is coated before the electrical connection support is placed near the end face of the cell stack, and the other layers of the encapsulation system are coated after the electrical connection support is placed near the end face.

32. The method of claim 19, further comprising: - Provide a frame (105) for forming multiple support members (5). - Place the frame near the first end face of a stack of multiple units, arranging these stacks into multiple rows and / or columns. - At least one cut is formed in the longitudinal and / or transverse directions of these stacks, thereby forming multiple electrochemical devices.

33. An energy-consuming device (1000) comprising a body (1002) and a battery according to any one of claims 1 to 18, the battery being capable of supplying energy to the energy-consuming device, and an electrical connection support (5) of the battery being fixed to the body.

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