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    • 专利摘要:
    An electrochemical device, such as a microbattery or an electrochromic system, comprising at least one stack of active layers (2) containing lithium, said stack (2) being arranged on a substrate (1) and being covered with a layer of encapsulation (13). The encapsulation layer (13) comprises at least: a barrier film (11) having at least one electrically insulating face and comprising at least one layer that is impermeable to the oxidizing species, said adhesive film (12) comprising a juxtaposition of adhesive electrically conductive strips (16) and electrically insulating adhesive strips (17), - an adhesive film (12), provided with a first face and a second face, the first face being in contact with the electrically face isolating the barrier film (11) and the second side covering the stack of active layers (2) and a portion of the substrate (1).
    公开号:FR3034571A1
    申请号:FR1552698
    申请日:2015-03-31
    公开日:2016-10-07
    发明作者:Messaoud Bedjaoui；Sylvain Poulet；Thomas Sebastien
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] An electrochemical device, such as a microbattery or an electrochromic system, covered by an encapsulation layer comprising a barrier film and an adhesive film, and a method of making such a device.
    [0002] TECHNICAL FIELD OF THE INVENTION The invention relates to an electrochemical device, such as a microbattery or an electrochromic system, covered by an encapsulation layer comprising a barrier film and an adhesive film, and a process for producing a such device. State of the art Microbatteries are defined as all solid electrochemical generators formed by an active stack of thin layers which constitute the electrodes (positive and negative) separated by an electrolyte. The positive electrode is formed of a material having good ionic conductivity, for example titanium oxysulfide (TiOS) or a lithiated metal oxide, such as Li0002, LiNiO2, LiMn204. The electrolyte is an electrical insulator having a high ionic conductivity such as lithium oxynitride and phosphorus (LiPON), LiSON, LiBON, Li2SO4, LiNb03 ... Finally, the nature of the negative electrode varies according to the technology of the microbattery. In "lithium-ion" microbatteries, the negative electrode consists of a lithiated material, that is to say a material into which lithium ions are inserted. In "lithium-metal" microbatteries, the negative electrode is exclusively formed of lithium. 3034571 2 The stack of the battery is completed by anodic and cathodic current collectors. However, lithium-containing materials are very sensitive to air, and in particular to oxygen and moisture. To prevent them from oxidizing, they must be covered with an inert and waterproof encapsulation system. The control of encapsulation is a key factor that determines the efficiency over time of microbatteries.
    [0003] The implementation of these encapsulation systems can be carried out in two different ways: thin-film encapsulation, also called monolithic encapsulation, and encapsulation by insert, also called heterogeneous encapsulation. In the case of monolithic encapsulation, the encapsulation layers are directly deposited on the electrochemical device. Heterogeneous encapsulation is a solution based on the postponement of a sealed hood with respect to the atmosphere. The latter case is considered one of the most robust solutions to effectively protect lithium microbatteries because of its ease of implementation, its low cost and its performance. In this technology, the encapsulation system is carried out separately before transferring it to the active layers of the microbattery. Figure 1 schematically shows a lithium microbattery with an insert encapsulation system as described in US2008 / 0003493. The microbattery comprises a stack 2 of active layers, formed on a substrate 1. The stack 2 is contained in a cavity 3 delimited by the substrate 1 and a cover 4 facing the substrate. The hood is, for example glass, ceramic or metal. A bead 5 of adhesive material, such as epoxy, secures the cover 4 to the substrate 1, around the stack of active layers 2. 3034571 3 To simultaneously maintain the cover 4 on the substrate, the adhesive bead 5 occupies a large area around the stack 2. A large area of the substrate is thus dedicated to the cavity 3 and the sealing bead 5 5, to the detriment of the useful surface of the microbattery. In another example of this document, illustrated in Figure 2, the cover 4 'is formed of a stack of three layers, two polymer layers enclosing a metal layer. The cover is disposed on the substrate and is secured to the substrate by rolling. To form batteries in large quantities, a network of microbatteries is formed on a single substrate. A bead of adhesive is disposed around each stack of active layers, and then a bonnet is formed on each stack. The resin is then polymerized to secure the covers to the substrate. In existing methods, each elementary microbattery is encapsulated individually. However, the substrates supporting the microbatteries may comprise from a few tens to a few thousand unit components. At present, such unit hood glue encapsulation methods are not suitable for producing a large microbattery volume.
    [0004] This problem is also found in electrochromic systems. Electrochromic devices, or electrochromic devices are devices that are colored by the action of an electric field. The devices have an architecture similar to microbatteries: they comprise an active electrode and a counter-electrode separated by an electrolyte. The active electrode is conventionally composed of an electrochromic material capable of reversibly and simultaneously inserting ions and electrons. The insertion of the ions must be reversible in order to obtain devices having a good stability in cycling.
    [0005] The active layers must also be protected from the atmospheric elements by an encapsulation system. It is found that there is a need to provide a lithium microbattery or a low clutter electrochromic system with a powerful and compact encapsulation device capable of being used to produce high speed devices. OBJECT OF THE INVENTION The object of the invention is to overcome the drawbacks of the prior art and, in particular, to propose an electrochemical device, such as a microbattery or an electrochromic system, having an efficient encapsulation device and compact and a method of making such a device, said method being able to be used to produce devices in large quantities. This object is achieved by an electrochemical device, such as a microbattery or an electrochromic system, comprising at least one stack of active layers containing lithium, said stack comprising at least a first electrode connected to a first current collector and at least one less second electrode connected to a second current collector, said stack being disposed on a substrate and being covered with an encapsulation layer.
    [0006] The encapsulation layer comprises at least: a barrier film having at least one electrically insulating face and comprising at least one layer that is impervious to oxidizing species; an adhesive film, provided with a first face; and a second face, the first face being in contact with the electrically insulating face of the barrier film and the second face covering the stack of active layers and a portion of the substrate, the adhesive film comprising a juxtaposition of electrically conductive adhesive strips and electrically insulating adhesive strips, wherein two electrically conductive strips are separated by an electrically insulating strip to be electrically insulated from each other, each electrically conductive strip being connected to the first current collector or the second current collector of the stack of active layers.
    [0007] This object is also achieved by an encapsulation layer, configured to encapsulate at least one stack of active layers of an electrochemical device, disposed on a substrate, said encapsulation layer comprising a stack of layers comprising at least: a barrier film having at least one electrically insulating face and comprising at least one layer which is impervious to oxidizing species; - an adhesive film, provided with a first face and a second face, the first face being in contact with each other; with the electrically insulating face of the barrier film, the adhesive film comprising a juxtaposition of electrically conductive adhesive strips and adhesive electrically insulating strips, two electrically conductive strips being separated by an electrically insulating strip to be electrically insulated from each other each electrically conductive strip being connected to the first current collector or at the second current collector of the stack of 30 active layers.
    [0008] This object is also achieved by a method for producing an electrochemical device, such as a microbattery or an electrochromic system, comprising the following successive steps: providing a substrate on which at least one stack of 5 active layers is placed; said stack comprising at least a first electrode connected to a first collector and at least a second electrode connected to a second collector, - providing a barrier film and an adhesive film o the barrier film having at least one electrically insulating face and comprising at least least one layer that is impervious to the oxidizing species, wherein the adhesive film is provided with a first face and a second face, the adhesive film comprising a juxtaposition of adhesive electrically conductive strips and electrically insulating adhesive strips, two electrically conductive strips being separated by an electrically insulating strip for being electrically insulated from each other, - securing the barrier film and the adhesive film with the substrate, so as to encapsulate the stack of active layers, the barrier film and the adhesive film forming an encapsulation layer, the first face of the adhesive film being in contact with the electrically insulating face of the barrier film and the second face of the adhesive film being intended to be in partial contact with the substrate, the adhesive film covering the stack of active layers and a part of the substrate, each strip of electrically conductive material being connected to the first or second collectors of the stack of active layers.
    [0009] Other advantages and features will become more clearly apparent from the following description of particular embodiments of the invention given by way of non-limiting example and shown in the accompanying drawings, in which: FIGS. 1 and 2 diagrammatically show, in section, lithium microbatteries according to the prior art; FIG. 3 schematically represents, in section, a micro-battery, FIGS. schematically and in top view several microbatteries arranged on a substrate, according to various embodiments, - Figure 6 schematically shows, in section, an encapsulation layer according to a particular embodiment of the invention, - FIGS. 7 to 9 show, schematically and in section, several microbatteries covered by an encapsulation layer according to various Embodiments, FIG. 10 schematically shows, in top view, an encapsulation layer according to a particular embodiment of the invention; FIG. 11 is a diagrammatic and top view of several microbatteries; arranged on the same substrate and covered by an encapsulation layer according to one embodiment of the invention, FIG. 12 is a diagrammatic sectional view of two microbatteries covered by a mode-encapsulation layer. particular embodiment.
    [0010] DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION The method of producing an electrochemical device, such as a microbattery or an electrochromic system, comprises the following successive steps: (i) providing a substrate 1 on which is disposed at least one stack of active layers 2 containing lithium, said stack comprising at least a first electrode connected to a first current collector and at least a second electrode connected to a second current collector, (ii) providing a barrier film 11 and an adhesive film 12 o the barrier film 11 having at least one electrically insulating face and comprising at least one layer that is impervious to oxidizing species, where the adhesive film 12 is provided with a first face and a second face, (iii) optionally, forming through apertures 19 through the barrier film 11, (iv) securing the barrier film 11 and the adhesive film 1 2 with the substrate, so as to encapsulate the stack of active layers 2, the first face of the adhesive film being in contact with the electrically insulating face of the barrier film 11 and the second face of the adhesive film being intended to be in contact with each other. part with the substrate, the barrier film 11 and the adhesive film 12 forming an encapsulation layer 13.
    [0011] Advantageously, the adhesive film 12 continuously covers the stack of active layers 2 and a portion of the substrate 1. Preferably, the interface between the barrier film 11 and the substrate 1 forms a continuous ring around the stack of active layers. 2.
    [0012] Step (i) requires the provision of a substrate on which is disposed at least one stack of active layers 2 containing lithium, ie a microbattery devoid of encapsulation layer 13. FIG. 3 schematically represents a lithium microbattery . The microbattery conventionally comprises a stack 2 of active layers deposited on one side of a substrate 1. The stack of active layers 2 comprises at least a first electrode and a second electrode: a negative electrode 6 (anode) and a positive electrode. 7 (cathode).
    [0013] The positive electrode 7 is formed of a layer of lithium insertion material, such as TiOS, TiS2, LiTiOS, LiTiS2, Li0002, V205 .... The anode 6 is formed of a material consisting exclusively of lithium metal (Li-metal battery) or a lithium-ion insertion material (Ni02, SnO, Si, Ge, C ...). The stack of active layers 2 also comprises a layer of lithium electrolyte 8 located between the two electrodes. The electrolyte layer 8 is preferably composed of lithium oxynitride and phosphorus (LiPON). It could also be in LiPONB, LiSiCON.
    [0014] The encapsulation layer 13 aims to protect the active layers of the oxidation, and more particularly the electrode 6 located at the top of the stack of active layers 2, opposite the substrate 4. The upper electrode is indeed the active layer most exposed to 25 oxidizing species. It is also the one that, in general, contains the most lithium, namely the anode. This particular configuration of the electrodes makes the encapsulation step even more critical. The microbattery also comprises current collectors: a cathode current collector 9 and an anode current collector 10. The current collectors 3034571 are of a metallic nature (titanium, gold, platinum aluminum, tungsten for example) and arranged on the host substrate 1. The host substrate 1 may be made of silicon, glass, or any other type of suitable material as a support for the production of microbatteries.
    [0015] Stacking can be carried out any technique known to those skilled in the art. The encapsulation process can be performed on a single microbattery. It can also be used to encapsulate several microbatteries simultaneously: several stacks of active layers, arranged on the same host substrate 1, are encapsulated simultaneously by a same encapsulation layer. The microbatteries can be arranged to be connected in parallel or in series.
    [0016] FIG. 4 is a diagrammatic representation, seen from above, of an electrochemical device comprising a plurality of active layer stacks 2 (here a group of six batteries) arranged on the same host substrate 1. Stacks of active layers 2 are arranged in the same plane parallel to the surface of the substrate. The stacks are not superimposed on each other along an axis perpendicular to the surface of the substrate. Stacks of active layers may be connected in parallel: the first electrically conductive strip connects the first current collectors of the active layer stacks and the second electrically conductive strip connects the second current collectors of the active layer stacks. For example, a first electrically conductive strip may be arranged to connect only the anode current collectors of the active layer stacks.
    [0017] A second electrically conductive strip may be arranged to connect only the cathode current collectors of the active layer stacks.
    [0018] According to another embodiment, the electrochemical device comprises several stacks of active layers, so as to form microbatteries arranged in series (FIG. 5). Each electrically conductive strip connects a first current collector of a stack of active layers with a second current collector of another stack. For example, an electrically conductive strip can connect an anode current collector of a first active layer stack with a cathode current collector of a second active layer stack.
    [0019] These configurations are given for illustrative purposes. A different number of microbatteries can be used. Step (ii) is to provide the barrier film 11 and the adhesive film 12. The barrier film 11 and the adhesive film 12, once assembled, will form the encapsulation layer 13. These films are formed and / or assembled regardless of the formation of the active layers on the substrate.
    [0020] The barrier film 11 is electrically insulating and comprises at least one sealing layer with respect to the oxidizing species. The barrier film 11 is advantageously chosen both for these barrier properties but also for these mechanical properties. It may be a monolayer film, i.e. the barrier film is formed of a single layer.
    [0021] According to a preferred embodiment, the barrier film 11 is a multilayer film: it is formed of a stack of layers of different natures. The stack of layers is oriented along an axis perpendicular to the surface of the substrate 1.
    [0022] The layer or layers forming the barrier film 11 are advantageously made of metal or of dielectric material. These materials have good barrier properties to the oxidizing elements present in the atmosphere (H2O, N2, O2).
    [0023] The performance of the protective barrier is defined by the permeation rate of the oxidizing species. For lithium microbatteries, the desired barrier level is generally between 10-4 and 10-5 g / m2 / day. The barrier level is advantageously less than 10-4 g / m 2 / day.
    [0024] When the barrier film 11 is a monolayer film, the dielectric material is, for example, glass, ceramic, mica or any dielectric material that can be made in a thin layer and can form a barrier to the oxidizing species. Advantageously, a monolayer barrier film made of glass, mica or ceramic, for example, acts as a cover. Such covers may be made in the form of strips having thicknesses less than 50 μm. Such thicknesses are advantageously compatible with rolling processes.
    [0025] In the case of a multilayer stack, the first layer of the barrier film is a layer of dielectric material. By first layer of the barrier film is meant the layer disposed between the adhesive film 12 and the other layers of the stack of the barrier film 11.
    [0026] In the case where the barrier film comprises at least two layers, the barrier film advantageously comprises a barrier layer of metal, such as aluminum, and an insulating layer, for example, made of polymer, for, advantageously, isolate the metal layer from the adhesive film. The insulating layer does not necessarily have oxidizing species barrier properties.
    [0027] The metal thin layers can be coupled to thin layers of thermoplastic material. Thin films, or thin metal foils, advantageously have good barrier properties against oxidizing species. The thin metal layers are, for example, aluminum-based material or steel-based, optionally coated with one or more layers of alloy (tinplate, black iron, chrome iron, stainless steel, etc.). .).
    [0028] Advantageously, the thin layers of thermoplastic material reinforce the mechanical strength of the barrier film 11. The thermoplastic polymers are preferably chosen from PEN (polyethylene naphthalate), PP (polypropylene), PET (polyethylene terephthalate), PC (Polycarbonate), PI ( Polyimide), PES (polyethersulphone). It may be another polymer adapted to multilayer structures. According to another embodiment, these polymers may be coated with one or more external layers (aluminum, copper, silver, SiOx, Al0x, etc.) or with one or more internal layers (inclusion of mineral fillers, additions of absorbers oxidant).
    [0029] The polymer coating is intended to improve the barrier properties of the polymers with respect to oxidants. The thermal properties are also improved. The polymer / coating assembly can thus withstand temperatures up to 200 ° C, allowing the use of a greater number of assembly methods.
    [0030] The thicknesses of the various metallic thin layers and thermoplastic thin layers are advantageously less than 300 μm. Advantageously, the thickness of the adhesive layers is at least equal to the thickness of the stack of active layers 2. According to a preferred embodiment, the barrier film 11 of the encapsulation layer 13 is obtained by rolling process. a PET thin film, 15 μm thick, on an aluminum thin film, 15 μm thick. The other part forming the encapsulation layer 13 is an adhesive film 12. The role of the adhesive part is to ensure the connection by direct bonding of the barrier film 11 to the host substrate 1 containing the components to be encapsulated. In addition to its adhesive role, the adhesive portion of polymeric material advantageously absorbs the volume variations of the microbattery during charging and discharging cycles. The adhesive portion of the encapsulation system has a thickness of a few microns to a few tens of microns. These relatively thin thicknesses advantageously make it possible to completely cover the flanks of the microbattery and to limit the lateral diffusion of the oxidants. This diffusion is particularly reduced with the electrically conductive strips, formed of doped polymer layers by addition of metal inclusions reinforcing the barrier properties of the polymers. The thickness of the adhesive portion is also chosen according to the surface topography of the components to be encapsulated. The adhesive film is preferably formed by a juxtaposition of adhesive electrically conductive strips and electrically adhesive insulating strips along an axis which is parallel to the surface of the substrate which supports the stack. By juxtaposition, it is meant that the strips are arranged next to one another, that they do not overlap and that there is no space between the strips, so as to form a continuous film. The electrically insulating strips and the electrically conductive strips are alternated, in a direction parallel to the surface of the substrate 1. At least a first and a second strip of electrically conductive material are separated by at least one strip of electrically insulating material. The first and second strips of electrically conductive material are electrically isolated from each other. Figure 6 is a schematic representation of the principle of juxtaposition of electrically conductive strips 16 and electrically insulating strips 17. Other architectures, arrangements of electrically conductive strips 16 and insulators can be envisaged. The arrangement of the electrically conductive strips 16 and the electrically insulating strips 17 must be made to match some or all of the electrically conductive strips 16 with some or all of the ranges of the current collectors 9, 10 of the components. to protect. Each strip of electrically conductive material is connected to the first or second current collector of the stack. There are therefore at least first and second strips of electrically conductive and adhesive material which are connected, respectively, to the first electrode and the second electrode of the active layer stack 2 via the current collectors.
    [0031] The electrically conductive and insulating strips 16 are chosen not only for their bonding and adhesion properties but also for their chemical and mechanical compatibilities with the layers of the barrier film 11 of the encapsulation layer 13.
    [0032] The adhesion strength is, for example, between 1N / cm and 10N / cm. The electrically insulating 17 and conductive strips advantageously have identical thicknesses as well as identical or even identical elastic and thermal properties in order to increase the life of the device. By identical, we mean up to 5%. The electrically insulating strips 17 have an electrical resistivity greater than 1090 m. They can be obtained from thermoplastic (polyethylene, polyimide, etc.) or thermosetting (silicone, epoxide, etc.) polymer films, for example by UV or thermal treatment. The electrically conductive strips 16 have an electrical conductivity greater than 102S.m-1. The conductive strip is preferably made of conductive polymer. Even more preferably, the electrically conductive strip is made of adhesive conductive polymer. The conductive polymer may be intrinsically conductive. In this case, it is advantageously chosen from polyacetylene, polythiophene, polypyrole and phenylene polysulfide. According to another alternative, the conductive polymer is formed from an insulating polymer doped with metal charges (silver, copper, platinum, etc.) or conductive carbonaceous ones. According to a particular embodiment, the adhesive parts have adhesive properties on the two main faces, i.e. the first face 30 intended to be in contact with the barrier film 11 and the second face intended to be in contact with the substrate.
    [0033] This embodiment is preferable in the case where the barrier and adhesive films are rolled together. The adhesive, insulating or conductive parts may be, for example, in the form of double-sided tapes based on acrylic, silicone, rubber or a mixture of these materials.
    [0034] By way of example, it is possible to use 25 μm thick Tesa60260 conductive adhesives coupled with Tesa61562 insulating adhesives 25 μm thick to produce, respectively, the electrically conductive strips 16 and insulators of the part. adhesive. These adhesives are marketed by the company Tesa. Other types of adhesive tapes can be used to develop the adhesive parts of the encapsulation systems. We can cite, as an indication and not exhaustive, the adhesives marketed by Henkel: Ablefilm ECF550, Ablefilm ECF561E, Ablefilm 563K, etc. or marketed by 3M: 1007N, 8006C, 3007, 9703 ... The adhesive polymers can also be pressure-sensitive polymers (pressure sensitive adhesive). The choice of materials is made so as to obtain good chemical compatibility between the adhesive tapes and the active layers of the components to be encapsulated. For example, in the case of real surface components 1 cm × 1 cm, spaced apart by 1 mm on wafers of 200 mm, the electrically insulating strips have a width and a length of 0.8 cm × 20 cm and the electrically conductive strips have a thickness of width and a length of 0.5cmx20cm. According to a particular embodiment, the adhesive film comprises traps of oxidizing species such as for example water ("getters" in English).
    [0035] These traps can be used in the manufacture of electrically conductive strips 16 and / or electrically insulating strips 17.
    [0036] The materials of said traps may be, for example, mixed with the materials forming said strips. By way of non-limiting and exhaustive description, the getters may consist of a material chosen from zeolites, silica, alumina, alkali metal oxides, metals or their alloys. The realization of the getters can be adapted according to the methods of producing electrically insulating and electrically conductive strips. The getters can be in the form of wire, ribbon, powders or thin layers. At the level of the method of implementation, one skilled in the art can choose between the different techniques of the state of the art such as, for example, centrifugal deposition processes, gel deposition or other methods. deposition of thin layers (chemical vapor deposition (CVD), physical vapor deposition (or PVD) ...).
    [0037] To perform step (iv), the barrier film 11 and the adhesive film 12 may be, according to a first embodiment, assembled together before being secured to the substrate. In this case, the encapsulation layer 13 is reported in a single step on the substrate.
    [0038] According to another embodiment, the assembly of the encapsulation layer 13 is carried out in two successive postponements: a first step to postpone the adhesive film 12 and a second step to postpone the barrier film 11. The adhesive film 12 is solidarisé, at first, with the substrate. The barrier film 11 is assembled, subsequently secured to the adhesive film 12.
    [0039] The postponement of the encapsulation layer 13 in a single step requires previously to secure the adhesive film 12 with the barrier film 11, in order to form the encapsulation layer. The encapsulation layer will then be transferred to the substrate 1.
    [0040] The adhesive film 12, formed of conductive and insulating adhesive strips juxtaposed to each other, can be associated with the barrier film 11 by dispensing, rolling or coating, so as to form the encapsulation layer 13.
    [0041] Preferably, the barrier portion and the adhesive portion are laminated together. The encapsulation layer 13 obtained is shown in FIG. 6. The encapsulation layer 13 is configured to encapsulate at least one stack of active layers 2 of the electrochemical device disposed on a substrate 1. The encapsulation layer 13 comprises a stack of layers comprising at least: a barrier film having at least one electrically insulating face and comprising at least one layer that is impervious to the oxidizing species; an adhesive film 12 provided with a first face and a second face, the first face being in contact with the electrically insulating face of the barrier film 11, the adhesive film 12 comprising a juxtaposition of adhesive electrically conductive strips 16 and electrically insulating adhesive strips 17.
    [0042] At least first and second strips of electrically conductive material are separated by at least one strip of electrically insulating material, the first and second strips of electrically conductive material being electrically isolated from each other.
    [0043] The encapsulation layer 13 is advantageously self-supporting and conformable in order to be able to absorb the relief of the components placed on the substrate. By freestanding, we mean an element that is mechanically held in one piece during handling. The encapsulation layer, prepared independently of the active layers, can be reported on the active layers.
    [0044] By conformable, it is meant that the encapsulation layer has a substantially uniform thickness. According to the preferred embodiment, the encapsulation layer, also called encapsulation system or element, has a total thickness between 30pm and 100pm. The thermal properties (strength and coefficient of expansion), elasticity (Young's modulus) and flexibility of the adhesive film 12 and the barrier film 11 are advantageously comparable to avoid possible deformations of the encapsulation system during reporting processes. By comparable means, for example, that the expansion coefficients of the adhesive film 12 and the barrier film 11 do not exceed more than 5%. The compressibility properties of the two parts are also advantageously equivalent so as to avoid possible adhesion failure between the adhesive part and the barrier film part 11 or between the adhesive part and the devices to be encapsulated during the transfer of the adhesive part. encapsulation layer 13. Equivalent means that the compressibility properties do not differ by more than 5%.
    [0045] According to a particular embodiment, the encapsulation layer 13 may comprise, before being assembled on the host substrate 1, a protective film 21 (FIG. 6). The protective film 21 is disposed on the adhesive film 12. The protective film 21, also called "liner", advantageously makes it possible to mechanically consolidate the encapsulation layer 13, especially during the handling operations, before the transfer step, and protect the adhesive film 12. The protective film 21 is removed before the transfer of the encapsulation layer 13 on the host substrate 1.
    [0046] The protective film 21 is chemically inactive with respect to the adhesive film 12.
    [0047] The protective film is, for example, a film of polymeric material. For example, it may be a film made of PEN (polyethylene naphthalate), PP (polypropylene), PET (polyethylene terephthalate), PC (Polycarbonate), PI (Polyimide), PES (polyethersulphone). It has a thickness of some tens of microns. The encapsulation layer 13 is, for example, formed of a stack comprising: - a barrier film 11 formed of an aluminum / PET bilayer, 10 - an adhesive film 12 formed of a juxtaposition of electrically conductive and insulating strips 16 Tesa60260fTesa61562, a protective film 21. The encapsulation layer 13 has a total thickness of the order of 55 μm.
    [0048] According to a particular embodiment, the encapsulation layer 13 comprises traps of oxidizing species to improve and limit the problem of lateral permutation of the adhesive part.
    [0049] The encapsulation layer 13 is then transferred to the substrate so as to encapsulate the active layers. The encapsulation layer, formed of the barrier film and the adhesive film, is secured to the substrate by rolling or by a sealing technique. Sealing means the transfer of the encapsulation layer onto the substrate 25 with at least partial bonding of the layer to the substrate, for example by welding associated with compression, thermocompression or UV treatment. Preferably, the encapsulation layer 13 is secured to the substrate 30 with a rolling method. This method makes it possible to efficiently assemble the various nested elements. It can be carried out under vacuum or under a controlled atmosphere. This step may be, for example, carried out in a glove box, the humidity and oxygen levels being less than 5 ppm, or even in an anhydrous clean room. The rolling conditions will be adjusted according to the nature of the adhesives used. For example, the assembly between an aluminum / PET / adhesive encapsulation layer 13 and the active components can be performed at a temperature of 90 ° C with a pressure above 1 bar and a speed below 3 m / min.
    [0050] According to another embodiment, the encapsulation layer 13 is secured to the substrate by crosslinking the adhesive film 12. The adhesive film 12 of the encapsulation layer 13 may be, in this case, a liquid polymer. Insulating and conductive liquid polymer strips are alternately deposited on the barrier film 11, for example by coating. The encapsulation layer 13 is transferred to the substrate. The adhesive film 12 is then crosslinked by irradiation under UV or by a heat treatment so as to secure the encapsulation layer 13 with the host substrate 1.
    [0051] In this configuration, the barrier film 11 is transparent to UV rays. The microbattery obtained is shown in FIGS. 7a, b and c. After having secured the encapsulation layer 13 with the substrate, contact reversals 18 are positioned at the side faces of the electrically conductive strips. The possibility of offsetting the contacts, outside the active zones, allows the realization of external connections of a set of batteries with other microelectronic devices. FIGS. 7a, 7b and 7c show various alternative embodiments in which the electrically insulating layer completely or partially covers the flanks of the active layers.
    [0052] The embodiment of FIG. 7a corresponds, advantageously, to the case where the electrically conductive strips are anisotropic films having a vertical conduction. In the other cases (FIGS. 7b and 7c), at least one of the flanks of each stack of active layers is completely covered, protected by an electrically insulating strip, so as to avoid short circuits within the device. As shown in FIG. 7b, the sidewalls of the active layer stacks are completely covered by an electrically insulating strip. According to a preferred embodiment, the method comprises an additional step (iii) of texturing at least the barrier film 11, and more particularly, to form through openings 19 through the barrier film 11. The through openings 19 may be of different sizes and shapes. As shown in Figure 8, two microbatteries are shown in section. The openings 19 partially pass through the encapsulation layer 13.
    [0053] In FIG. 8, the microbatteries are connected in series. The anode of the first microbattery is connected to the cathode of the second microbattery by the electrically conductive strip disposed in the center of the figure. The openings 19 formed through the barrier layer make it possible to carry out a contact recovery, through said openings 19, at the level of the stack of active layers, and thus to reach the first and second electrodes of the stack of layers. active. The electrically conductive strips, accessible through the openings 19 passing through the barrier layer, are used to perform the contact resets.
    [0054] To achieve such a configuration, the insulating and conductive adhesive strips, forming the adhesive film 12, are self-supporting by rolling or sealing on the host substrate 1 before the previously textured barrier film 11 is transferred, respecting the location of the ranges. contacting devices on the host substrate 1. Alternatively, the barrier film can be structured after being assembled with the substrate. The openings 19 are advantageously at the periphery of the device. The fact of offsetting the contact recovery at the periphery, in particular when several stacks are arranged on the same substrate, allows better 3D integration while allowing the transfer of other components to the encapsulation layer. These openings are positioned facing at least one conductive strip and / or at least one current collector according to the electrical routing made of the device. The periphery may be located a few millimeters, for example from 1 to 10 mm, from the stack of active layers, at the level of the current collectors. The geometry of the periphery will be chosen by those skilled in the art so as to be able to carry out the integration steps, such as welding, with other devices without altering the electrochemical properties of the batteries.
    [0055] According to another preferred embodiment, shown in FIG. 9, an electrically insulating layer 20 is deposited on the textured barrier layer. The flanks of the openings are, advantageously, both electrically insulated and protected from atmospheric oxidants and moisture. Lateral protection is, for example, improved by depositing an alumina base layer or a layer of alumina a few nanometers thick. It may be, for example, a highly consistent deposit made at low temperature by suitable deposition techniques such as the deposit of atomic thin layers (or ALD for "Atomic Layer Deposition"). Low temperature means temperatures below 100 ° C. The optimum temperature of the ALD process is of the order of 80 ° C.
    [0056] The electrically insulating layer 20 advantageously forms an electrical insulation if the barrier film 11 comprises one or more electrically conductive layers, such as metal layers.
    [0057] Preferably, the thickness of the electrically insulating layer 20 is between 10 nm and 50 nm. The alumina layer may be deposited before or after the assembly step. In another particular embodiment, through apertures 19 are made through the entire thickness of the encapsulation layer. The openings pass through not only the barrier film but also the adhesive film 12. The entire thickness of the encapsulation layer 13 is thus structured. FIG. 10 shows in bottom view an encapsulation layer 13 provided with through-openings 19.
    [0058] Once the encapsulation layer 13 has been postponed on the host substrate 1, the through-openings 19 form an access to the current collectors 9, 10 of the microbatteries, which facilitates the formation of the electrical contacts. FIG. 11 represents a host substrate 1 provided with six individual batteries and on which an encapsulation layer 13 has been reported. The encapsulation layer 20 is provided with through openings 19. The alignment step between the FIG. encapsulation 13 and the host substrate 1 is facilitated by the geometric correspondence between the openings and the current collectors 9, 10. The openings 19 are used to align the encapsulation layer, and thus the conductive and insulating strips, with the 25 different components of the substrate during the transfer stage. Advantageously, these openings allow to expel the air during assembly. The formation of bubbles between the encapsulation layer 13 and the active layers is thus avoided and the adhesion between the encapsulation layer 13 and the host substrate 1 is improved. The performance of the microbattery and its life are thus increased.
    [0059] The formation of the apertures can be accomplished by localized etching techniques, such as a laser process or mechanical removal method.
    [0060] FIG. 12 is a sectional view of a line of two batteries encapsulated by an encapsulation layer 13. The encapsulation layer comprises an aluminum and PET bilayer barrier film 11 and a barrier film 11 of conductive adhesives and insulators. The openings 19 completely traverse the encapsulation layer 13.
    [0061] The presence of the through-openings 19 offers the possibility of forming electrical contacts geometrically remote from the active elements. This advantage facilitates assembly processes and integration of batteries with external circuits.
    [0062] It is thus possible to couple the encapsulation and assembly operations of a set of batteries using a single process performed on the same host substrate 1 containing the different active elements connected in series or in parallel. .
    [0063] The encapsulation layer 13 obtained has: - good barrier performance: the desired barrier level is less than 10-4 and 10-5 g / m 2 / day, - good mechanical strength: the encapsulation layer presents, advantageously a Young's modulus less than 5GPa in order to be able to accommodate the volume variations of the microbattery, during the charging and discharging cycles. Otherwise, the expansion or contraction of the microbattery could lead to mechanical damage in the electrodes, resulting in an irreversible decrease in the electrical capacitance of physicochemical compatibility with lithium-containing materials. The formation of the encapsulation layer 13 does not damage the active layers.
    [0064] According to another embodiment, the electrochemical device is an electrochromic system. The "all solid" electrochromic system is in the form of a stack of thin solid layers on a substrate 1 (FIG. 3). In particular, the electrochromic device comprises, successively from the substrate 1, a counterelectrode 7, an ionic conducting electrolyte 8, an electrochromic active electrode 6. The electrochromic active electrode is formed of an electrochromic material capable of insert, reversibly and simultaneously, ions and electrons.
    [0065] Under the effect of a potential difference applied between the active electrode and the counter-electrode, the ions are inserted into the electrochromic material of the active electrode to give a persistent coloration of the corresponding oxidation state. . By applying reverse bias, the ions disengage from the active electrode which returns to its initial, colored or transparent oxidation state. The oxidation states of the electrochromic material therefore correspond to the inserted and uninserted states and are of a distinct color when subjected to an appropriate power supply.
    [0066] Before applying the potential difference, the color displayed is that of the substrate, obtained by transmittance through the stack. After applying a potential difference between the active electrode and the counter-electrode, a display of a different color corresponding to that of the electrochromic material of the active electrode is obtained.
    [0067] The encapsulation layer 13 is, in the case of electrochromic systems, transparent to light.
    [0068] The active electrode 6 and / or the counter-electrode 4 is an electrode made of tungsten oxide, iridium oxide, vanadium oxide or molybdenum oxide.
    [0069] Active electrode 6 is preferably tungsten oxide or molybdenum oxide. The solid layer of ionic conductive electrolyte 8 is based on lithium, for example, lithium nitride (Li3N), LiPON, LiSiPON or LiBON etc. The specific ion is, advantageously, the ion The Li + ion has a higher mobility than other ions such as sodium or silver because of the small size of the lithium ion, decreasing the response time of the electrochromic system. The counter-electrode 7 is, for example, in iridium oxide, vanadium oxide.
    [0070] The encapsulation layer 13 may be deposited with the same method on the electrochromic device. With the encapsulation method described above, it is possible to provide a simultaneous and grouped protection of a set of lithium-based components (microbattery and / or electrochromic device) by an encapsulation system. The encapsulation process is efficient and compatible with high volume production rates thus enabling a maximum of 30 components to be encapsulated simultaneously.
    [0071] Since it is possible to deport the electrical contacts of the components with respect to the location of the active layers on the host substrate, integration and interconnectivity operations are facilitated over commonly used methods.
    [0072] It is possible to encapsulate and assemble several lithium microbatteries of the same type, arranged in series or in parallel. The encapsulation process of the batteries in series or in parallel remains identical. The interconnection of several unitary batteries advantageously makes it possible to modulate the electric power of the system obtained by increasing the output voltage and / or the discharge capacity. The self-supporting stack can also be applied to a combination of microbatteries interconnected with other microelectronic devices (electrochromic, photovoltaic, ....) made on the same host substrate. This advantage responds particularly to the problem of realization of multifunctional autonomous systems.
    权利要求:
    Claims (29)
    [0001]
    REVENDICATIONS1. An electrochemical device, such as a microbattery or an electrochromic system, comprising at least one stack of active layers (2) containing lithium, said stack comprising at least a first electrode connected to a first current collector and to a second second connected electrode a second current collector, said stack (2) being arranged on a substrate (1) and being covered with an encapsulation layer (13), characterized in that the encapsulation layer (13) comprises at least: a barrier film (11) having at least one electrically insulating face and comprising at least one sealing layer with respect to the oxidizing species, an adhesive film (12) provided with a first face and a second face, the first face being in contact with the electrically insulating face of the barrier film (11) and the second face covering the stack of active layers (2) and a portion of the substrate (1), the adhesive film (12) comprising a jux taping electrically conductive adhesive strips (16) and adhesive electrically insulating strips (17), two electrically conductive strips being separated by an electrically insulating strip to be electrically insulated from each other, each electrically conductive strip being connected to the first current collector or the second current collector of the stack of active layers (2).
    [0002]
    2. Device according to claim 1, characterized in that the encapsulation layer (13) comprises apertures (19) passing through at least the barrier film (11), so as to allow a resumption of contact through the 3034571 31 openings (19), the openings being advantageously at the periphery of the device.
    [0003]
    3. Device according to one of claims 1 and 2, characterized in that the barrier film (11) is formed of a layer or more layers, the layer or layers being metal or dielectric material, the first layer said film being formed by a layer of dielectric material.
    [0004]
    4. Device according to one of claims 1 to 3, characterized in that the 10 electrically conductive strips (16) are adhesive conductive polymer.
    [0005]
    5. Device according to claim 4 characterized in that the electrically conductive strips (16) are adhesive conductive polymer, said conductive polymer being selected from polyacetylene, polythiophene, polypyrole, and phenylene polysulfide, or an insulating polymer doped with conductive metal or carbon charges.
    [0006]
    6. Device according to one of claims 1 to 5, characterized in that the adhesive electrically insulating strips are selected from thermoplastic materials or curable by UV or heat treatment.
    [0007]
    7. Device according to any one of claims 1 to 6, characterized in that the adhesive film (12) comprises traps of oxidizing species. 25
    [0008]
    8. Device according to any one of claims 1 to 7, characterized in that the encapsulation layer (13) has a thickness between 30pm and 100pm.
    [0009]
    9. Device according to any one of claims 1 to 8, characterized in that the barrier film (11) is covered with an electrically insulating layer (20). 3034571 32
    [0010]
    10. Device according to any one of claims 1 to 9, characterized in that the electrochemical device comprises several stacks of active layers disposed on the substrate (1), each electrically conductive strip connecting a first current collector of a stack active layers with a second current collector of another stack of active layers, so as to serially connect said stacks of active layers. 10
    [0011]
    11. Device according to any one of claims 1 to 9, characterized in that the electrochemical device comprises several stacks of active layers disposed on the substrate (1), the first electrically conductive strip connecting the first current collectors layer stacks. active, the second electrically conductive strip connecting the second current collectors active layer stacks, so as to connect in parallel the active layer stacks.
    [0012]
    An encapsulation layer (13), configured to encapsulate at least one stack of active layers (2) of an electrochemical device, disposed on a substrate (1), said encapsulation layer (13) comprising a stack of layers. comprising at least: - a barrier film (11) having at least one electrically insulating face and comprising at least one layer that is impervious to the oxidizing species, -an adhesive film (12), provided with a first face and a second face, the first face being in contact with the electrically insulating face of the barrier film (11), the adhesive film (12) comprising a juxtaposition of adhesive electrically conductive strips (16) and electrically insulating adhesive strips (17), two electrically conductive strips being separated by an electrically insulating strip to be electrically insulated from each other. 3034571 33
    [0013]
    13. Encapsulation layer according to claim 12, characterized in that the barrier film (11) is formed of one or more layers, the layer or layers being of metal or dielectric material, the first layer 5 of said film being formed by a layer of dielectric material.
    [0014]
    14. Encapsulation layer according to one of claims 12 and 13, characterized in that it has a thickness between 30pm and 100pm. 10
    [0015]
    15. Encapsulation layer according to any one of claims 12 to 14, characterized in that the barrier film (11) is provided with through openings (19). 15
    [0016]
    16. Layer according to any one of claims 12 to 15, characterized in that the barrier film (11) is covered with an electrically insulating layer (20).
    [0017]
    17. A method of producing an electrochemical device, such as a microbattery or an electrochromic system, comprising the following successive steps: providing a substrate (1) on which at least one stack of active layers (2) is arranged, said stack (2) comprising at least a first electrode connected to a first collector and at least a second electrode connected to a second collector, providing a barrier film (11) and an adhesive film (12) where the barrier film (11) having the at least one electrically insulating surface and comprising at least one sealing layer with respect to the oxidizing species, wherein the adhesive film (12) is provided with a first face and a second face, the adhesive film (12) comprising a juxtaposition of adhesive electrically conductive strips (16) and electrically insulating adhesive strips (17), two electrically conductive strips being electrically separated by a strip insulation to be electrically insulated from one another, - to secure the barrier film (11) and the adhesive film (12) with the substrate (1), so as to encapsulate the stack of active layers (2), the barrier film (11) and the adhesive film (12) forming an encapsulation layer (13), the first face of the adhesive film (12) being in contact with the electrically insulating face of the barrier film (11) and the second face the adhesive film (12) being intended to be in partial contact with the substrate (1), the adhesive film (12) covering the stack of active layers (2) and a portion of the substrate (1), each strip of electrically conductive material being connected to the first current collector or the second current collector of the active layer stack (2).
    [0018]
    18. The method of claim 17, characterized in that the barrier film 20 (11) and the adhesive film (12) are assembled together before being secured to the substrate (1).
    [0019]
    19. The method of claim 17, characterized in that the adhesive film (12) is secured, in a first step, with the substrate (1) and in that the barrier film (11) is subsequently assembled on the adhesive film (12).
    [0020]
    20. Process according to any one of claims 17 to 19, characterized in that the substrate (1) comprises several stacks of active layers (2) and in that a same encapsulation layer (13) is arranged simultaneously on the stacks. 3034571
    [0021]
    21. Method according to any one of claims 17 to 20, characterized in that the method comprises a step of texturing at least the barrier film so as to form openings (19) passing through the barrier film (11). 5
    [0022]
    22. The method of claim 21, characterized in that the texturing step is followed by a step of depositing an electrically insulating layer (20) so as to cover the flanks of the openings (19) formed at least in the barrier film (11). 10
    [0023]
    23. The method of claim 22, characterized in that the electrically insulating layer (20) is alumina.
    [0024]
    24. A method according to any one of claims 17 to 23, characterized in that the barrier film (11) and the adhesive film (12) are secured to the substrate (1) by rolling or by a sealing technique.
    [0025]
    25. A method according to any one of claims 17 to 24, characterized in that the barrier film (11) is formed of an aluminum layer and a polymer layer. 20
    [0026]
    26. A method according to any one of claims 17 to 25, characterized in that the electrically conductive strips (16) are adhesive conductive polymer. 25
    [0027]
    27. The method of claim 26, characterized in that the electrically conductive strips (16) are adhesive conductive polymer, said conductive polymer being selected from polyacetylene, polythiophene, polypyrole, and phenylene polysulfide, or an insulating polymer doped with conductive metal or carbon charges. 3034571 36
    [0028]
    28. Method according to any one of claims 17 to 27, characterized in that the adhesive electrically insulating strips are chosen from thermoplastic materials or curable by UV or heat treatment.
    [0029]
    29. Method according to any one of claims 17 to 28, characterized in that the adhesive film (12) comprises traps of oxidizing species.
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    同族专利:
    公开号 | 公开日
    EP3076453A1|2016-10-05|
    EP3076453B1|2017-09-13|
    US20160293905A1|2016-10-06|
    US10193110B2|2019-01-29|
    FR3034571B1|2017-05-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2166609A1|2008-09-16|2010-03-24|Commissariat a L'Energie Atomique|Lithium micro-battery comprising an encapsulating layer and method of manufacturing the same|
    KR20120076187A|2010-12-29|2012-07-09|제일모직주식회사|Anisotropic conductive film|
    FR3009437A1|2013-07-30|2015-02-06|Commissariat Energie Atomique|LITHIUM MICROBATTERY PROTECTED BY A HOOD|
    US7553582B2|2005-09-06|2009-06-30|Oak Ridge Micro-Energy, Inc.|Getters for thin film battery hermetic package|KR20170063239A|2015-11-30|2017-06-08|삼성에스디아이 주식회사|Flexible rechargeable battery|
    FR3050074B1|2016-04-07|2018-06-22|Commissariat A L'energie Atomique Et Aux Energies Alternatives|ELECTROCHEMICAL DEVICE, SUCH AS A MICROBATTERY, AND METHOD FOR PRODUCING THE SAME|
    US10727454B2|2016-11-16|2020-07-28|Pacesetter, Inc.|Battery with enhanced resistance to dendrite formation|
    FR3068826A1|2017-07-10|2019-01-11|StmicroelectronicsSas|THIN FILM BATTERY|
    CN109585904B|2017-09-29|2021-11-23|辉能科技股份有限公司|Flexible lithium battery|
    法律状态:
    2016-03-31| PLFP| Fee payment|Year of fee payment: 2 |
    2016-10-07| PLSC| Publication of the preliminary search report|Effective date: 20161007 |
    2017-03-31| PLFP| Fee payment|Year of fee payment: 3 |
    2018-03-29| PLFP| Fee payment|Year of fee payment: 4 |
    2019-11-29| ST| Notification of lapse|Effective date: 20191106 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1552698A|FR3034571B1|2015-03-31|2015-03-31|ELECTROCHEMICAL DEVICE, SUCH AS A MICROBATTERY OR AN ELECTROCHROME SYSTEM, COVERED BY AN ENCAPSULATION LAYER COMPRISING A BARRIER FILM AND AN ADHESIVE FILM, AND METHOD OF MAKING SUCH A DEVICE.|FR1552698A| FR3034571B1|2015-03-31|2015-03-31|ELECTROCHEMICAL DEVICE, SUCH AS A MICROBATTERY OR AN ELECTROCHROME SYSTEM, COVERED BY AN ENCAPSULATION LAYER COMPRISING A BARRIER FILM AND AN ADHESIVE FILM, AND METHOD OF MAKING SUCH A DEVICE.|
    EP16163287.2A| EP3076453B1|2015-03-31|2016-03-31|Electrochemical device, such as a microbattery or an electrochromic system, covered with an encapsulation layer comprising a barrier film and an adhesive film, and method for manufacturing same|
    US15/086,717| US10193110B2|2015-03-31|2016-03-31|Electrochemical device, such as a microbattery or an electrochromic system, covered by an encapsulation layer comprising a barrier film and an adhesive film, and method for fabricating one such device|
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