Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
  • H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/0468—Compression means for stacks of electrodes and separators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/0436—Small-sized flat cells or batteries for portable equipment
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/0481—Compression means other than compression means for stacks of electrodes and separators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
  • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
  • H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/121—Organic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
  • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
  • H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
  • H01M50/133—Thickness
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/531—Electrode connections inside a battery casing
  • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
  • H01M50/552—Terminals characterised by their shape
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/543—Terminals
  • H01M50/562—Terminals characterised by the material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/572—Means for preventing undesired use or discharge
  • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
  • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/572—Means for preventing undesired use or discharge
  • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
  • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/14—Cells with non-aqueous electrolyte
  • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/14—Cells with non-aqueous electrolyte
  • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
  • H01M6/188—Processes of manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/40—Printed batteries, e.g. thin film batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to batteries, in particular to thin film batteries, and more particularly to the encapsulation systems which protect them. It presents a new encapsulation system which more effectively protects the areas of the battery which are located near the contact members.
• the invention relates more particularly to the field of lithium ion batteries, which can be encapsulated in this way.
• the invention also relates to a new process for manufacturing thin-film batteries, having a novel architecture and encapsulation which gives them a particularly low self-discharge and an improved service life.
• lithium ion batteries are very sensitive to humidity.
• the market requires a lifespan of more than 10 years; it is necessary to provide an encapsulation which makes it possible to guarantee this lifetime.
• Thin-film lithium ion batteries are multilayer stacks that include layers of electrodes and electrolyte, the thickness of which is typically between about one ⁇ m and about ten ⁇ m. They can comprise a stack of several elementary cells. It is observed that these batteries are sensitive to self-discharge. Depending on the positioning of the electrodes, in particular the proximity of the edges of the electrodes for multilayer batteries and the cleanliness of the cutouts, a leakage current may appear on the ends, a creeping short circuit which decreases the performance of the battery. This phenomenon is exacerbated if the electrolyte film is very thin.
• the cyclical variation in the volume of the anode materials also induces a cyclical variation in the volume of the battery cells. It thus generates cyclic stresses on the encapsulation system, liable to initiate cracks which are the cause of the loss of tightness (or even of integrity) of the encapsulation system. This phenomenon is another cause of the decrease in the performance of the battery during its life.
• lithium ion batteries are very sensitive to air and in particular to humidity.
• Mobile lithium ions react spontaneously with traces of water to form LiOH, leading to calendar aging of the batteries.
• All lithium ion conductive insert materials and electrolytes are not reactive with moisture.
• Li 4 Ti 5 O 12 does not deteriorate on contact with the atmosphere or traces of water.
• the inserted lithium surplus (x) is, for its part, sensitive to the atmosphere and reacts spontaneously with traces of water to form LiOH. The reacted lithium is then no longer available for storing electricity, leading to a loss of battery capacity.
• Document US 2002/0 071 989 describes a system for encapsulating an entirely solid thin film battery comprising a stack of a first layer of a dielectric material chosen from alumina (Al 2 O 3 ), silica (SiO 2 ), silicon nitride (Si 3 N 4 ), silicon carbide (SiC), tantalum oxide (Ta 2 O 5 ) and amorphous carbon, from a second layer of a dielectric material and a sealing layer disposed on the second layer and covering the entire battery.
• a dielectric material chosen from alumina (Al 2 O 3 ), silica (SiO 2 ), silicon nitride (Si 3 N 4 ), silicon carbide (SiC), tantalum oxide (Ta 2 O 5 ) and amorphous carbon
• a first proposed system comprises a layer of parylene covered with an aluminum film deposited on the active components of the battery. However, this system of protection against the diffusion of air and water vapor is only effective for about a month.
• a second proposed system comprises alternating layers of parylene (500 nm thick) and metal (about 50 nm thick). The document specifies that it is preferable to coat these batteries with a further Ultraviolet (UV) cured epoxy layer to reduce the rate of degradation of the battery by atmospheric elements.
• UV Ultraviolet
• the Applicant has also proposed, in document WO 2019/215 410, various examples of layers, intended to form respectively anodic and cathodic contact members.
• first example there is a first thin layer deposited by ALD, in particular of a metallic nature.
• second layer of epoxy resin charged with silver is provided.
• the first layer is a material loaded with graphite, while the second layer comprises metallic copper obtained from an ink loaded with nanoparticles.
• the surface of these welds exposed to the atmosphere remains very small, and the rest of the packaging consists of aluminum sheets sandwiched between these polymer sheets.
• two aluminum sheets are associated in order to minimize the effects linked to the presence of holes or defects in each of these aluminum sheets. The probability that two defects on each of the strips are aligned is greatly reduced.
• the encapsulation system must be watertight and hermetic, must envelop and completely cover the component or battery, and must also enable the edges of electrodes of opposite signs to be galvanically separated in order to avoid any creeping short circuit.
• An objective of the present invention is to remedy at least in part the drawbacks of the prior art mentioned above.
• Another object of the present invention is to provide lithium ion batteries with a very long life and having low self-discharge.
• the encapsulation system according to the invention is advantageously of the rigid type.
• the battery cells are rigid and dimensionally stable, linked to the initial choice of materials.
• the encapsulation system obtained in accordance with the invention is effective.
• the invention provides for producing an encapsulation system which can and which is advantageously deposited under vacuum.
• the batteries in accordance with the invention do not contain polymers; on the other hand, they can contain ionic liquids. In fact, they are either entirely solid or of the “quasi-solid” type in which case they include an electrolyte based on a nanoconfined ionic liquid base. From an electrochemical point of view, this nanoconfined liquid electrolyte behaves like a liquid, insofar as it provides good mobility to the cations which it conducts. From a structural point of view, this nanoconfined liquid electrolyte does not behave like a liquid, because it remains nanoconfined and can no longer leave its prison even during a treatment under vacuum and / or at high temperature.
• the batteries according to the invention which contain an electrolyte based on nanoconfined ionic liquid can consequently undergo treatments under vacuum, and / or under vacuum and at high temperature, with a view to their encapsulation.
• the edges of the layers can be exposed by cutting; after impregnation, these slices are closed by making the electrical contact.
• the method according to the invention is also well suited to the covering of mesoporous surfaces.
• At least one of the above objectives is achieved by means of at least one of the objects according to the invention as presented below.
• the present invention proposes as successive objects a battery, its manufacturing process, as well as an energy consuming device according to the appended claims.
• the present invention proposes as a first object a battery comprising: at least one elementary cell, said elementary cell successively comprising an anode current collector substrate, an anode layer, a layer of an electrolyte material or of a separator impregnated with an electrolyte, a cathode layer, and a cathodic current collector substrate, an encapsulation system covering at least part of the outer periphery of said elementary cell, the encapsulation system comprising:
• a first covering layer (2) preferably chosen from parylene, type F parylene, polyimide, epoxy resins, acrylates, fluorinated polymers, silicone, polyamide, sol-gel silica , organic silica and / or a mixture of these, deposited on the battery,
• each of the anodic and cathodic contact members comprises: a first electrical connection layer, arranged on at least the anodic connection zone and at least the cath
• the invention includes, in its second electrical connection layer, a metal foil.
• a metal sheet advantageously has a structure of the “self-supporting” type, or “free standing” in the English language. In other words, it is then carried out “ex situ”, then added to the vicinity of the first layer above.
• This metal foil can be obtained, for example by rolling; in this case, this laminated sheet may have undergone a final softening annealing, partial or total.
• the metal foil, used in the invention can also be obtained by other methods, in particular by electrochemical deposition or electrodeposition. In this case, it can typically be carried out “ex situ” as above. Moreover, by way of a variant, it can also be carried out “in situ”, that is to say directly on the first layer above.
• this metal sheet has a controlled thickness.
• the layer comprising metallic copper obtained from an ink loaded with nanoparticles which is described in WO 2019/215410 discussed above, is in no way a metallic foil within the meaning of the invention. Indeed, the layer of this prior document does not meet any of the above criteria.
• this metal foil typically is between 5 and 200 micrometers.
• this metal sheet is perfectly dense and electrically conductive.
• nickel, stainless steel, copper, molybdenum, tungsten, vanadium, tantalum, titanium, aluminum, chromium as well as the alloys comprising them.
• the use of such a metal foil provides significant advantages, compared with the solutions of the state of the art described above.
• the metal foil first of all confers a markedly improved seal, compared with a deposit of metal nanoparticles.
• the films obtained by sintering contain more point defects, which makes them less hermetic.
• the surfaces of metal nanoparticles are often covered with a thin layer of oxide, which is such as to limit their electrical conductivity.
• the use of a metal foil makes it possible to improve the airtightness as well as the electrical conductivity.
• the invention makes it possible to increase the life of the battery, in particular by virtue of a reduction in the coefficient of air permeation (Water Vapor Transmission Rate, WVTR) at the level of the contact members.
• WVTR Water Vapor Transmission Rate
• the metal foil is of the self-supporting type, this metal foil being advantageously attached to said first electrical connection layer, the foil metal is produced by rolling or by electrodeposition, the thickness of the metal sheet is between 5 and 200 micrometers, this metal sheet being in particular made from one of the following materials: nickel, stainless steel, copper, molybdenum, tungsten, vanadium, tantalum, titanium, aluminum, chromium as well as the alloys comprising them, each of the anodic and cathodic contact members comprises a third electrical connection layer comprising a conductive ink disposed on the second electrical connection layer.
• an electrical connection support made at least in part of a conductive material, which support is provided in the vicinity of a front face of an elementary cell, electrical insulation means, making it possible to mutually isolate two distant regions of this connection medium, these distant regions forming respective electrical connection paths
• said anode contact member making it possible to electrically connect a first lateral face of each elementary cell with a first electrical connection path
• said cathodic contact element makes it possible to electrically connect a second lateral face of each elementary cell with a second connection path electrical
• the electrical connection support is of the single-layer type, in particular a metal grid or a silicon interposer, the electrical connection support of the multilayer type, and comprises several layers arranged one below the other, this support being in particular of the type printed circuit
• said battery is a lithium ion battery
• the subject of the invention is also a method of manufacturing a battery comprising: at least one elementary cell, said elementary cell successively comprising an anode current collector substrate, a layer of 'anode, a layer of an electro
• a first electrical connection layer of material charged with electrically conductive particles said first layer being preferably formed of polymeric resin and / or of a material obtained by a sol-gel process loaded with electrically conductive particles, • optionally, when said first layer is formed of polymeric resin and / or of a material obtained by a sol-gel process loaded with electrically conductive particles, a drying step followed by a step of polymerization of said polymeric resin and / or of said material obtained by a sol-gel process,
• the metal foil is formed by rolling, then this metal foil thus formed is attached to the first electrical connection layer.
• the metal foil directly by electrodeposition, either ex situ or in situ relative to the first metallic connection layer the method comprises after step g), on at least the anodic and cathodic connection areas of the battery, coated with the first and the second electrical connection layer, a step h) of depositing a conductive ink said electrically insulating material is chosen from Al 2 O 3 , SiO 2 , SiO y N x , and epoxy resins
• the second layer covering comprises parylene N
• the thickness of the first covering layer is between 1 ⁇ m and 50 ⁇ m, preferably about 10 ⁇ m and in that the thickness d e the second covering layer is less than 200 nm, preferably between 5 nm and 200 nm, and even more preferably around 50 nm
• the sealing means are coated after having put in place the electrical connection support
• the attached figures schematically show multilayer batteries encapsulated according to different embodiments of the invention. They correspond to cross sections perpendicular to the thickness of the layers.
• FIG. 1 shows a battery comprising an encapsulation system according to the invention which is formed of two superimposed layers.
• Figure 2 shows a battery comprising a similar encapsulation system which comprises two successions of two layers.
• FIGS. 3 and 4 are perspective views showing alternating stacks of anode and cathode sheets, involved in two variants of a method for manufacturing a battery according to the invention.
• Figure 5 is a longitudinal sectional view, illustrating the battery of Figure 1 further including a conductive support.
• FIG. 6 is a view in longitudinal section, illustrating an alternative embodiment of FIG. 5.
• FIG. 7 is a top view, illustrating a frame allowing the simultaneous production of several batteries according to FIG. 5 or 6.
• FIG. 8 is a front view, similar to FIG. 5, illustrating a step in producing the battery which is represented in this FIG. 5.
• FIG. 9 is a top view, illustrating cutouts made on the frame of FIG. 7, so as to obtain a plurality of batteries.
• FIG. 10 is a front view, illustrating the integration of the battery of FIG. 5 on an energy consuming device.
• FIG. 11 is a front view, similar to FIG. 10, illustrating an alternative embodiment of this FIG. 10, in particular as regards the structure of the conductive support.
• FIG. 12 is a perspective view, illustrating in an exploded manner the various components of the conductive support of FIG. 11. Description of the invention
• the present invention applies to a so-called elementary electrochemical cell, that is to say to a stack 1 successively comprising an anode current collector, an anode layer, a layer of an electrolyte material or a separator. impregnated with an electrolyte, a cathode layer and a cathode current collector. Said collector is here also called “collector substrate”, namely anodic collector substrate and cathodic collector substrate.
• the present invention also applies to a battery comprising a stack of several elementary cells.
• the orthogonal frame of reference XYZ has been taken, for which the axis XX is a first horizontal axis, that is to say that it is included in the plane of the various constituent layers of the stack. Moreover, this axis XX is called transverse, namely that it extends laterally with reference to the sheet.
• the YY axis is a second horizontal axis, also included in the plane of the layers of the stack. This YY axis is called sagittal, ie it extends from back to front of the leaf. In particular, it is parallel to the plane of the contact members. Finally, the ZZ axis extends vertically, being perpendicular to each of the above axes. It is also referred to as the frontal axis.
• the battery is generally designated by the numeral I.
• the numeral 10 designates generally a sectional view of battery I on which we would see the alternate “open” layers which form stack 1 of the battery. Conventionally, this stack is for example a “mille-feuille” formed by a succession of layers of anode collector / anode / electrolyte or impregnated separator / cathode / cathode collector.
• this treatment can be a thermocompression treatment, comprising the simultaneous application of a pressure and a high temperature
• this stack is encapsulated by depositing an encapsulation system 4 to ensure the protection of the battery cell with respect to the atmosphere.
• the encapsulation system must be chemically stable, withstand high temperature and be impermeable to the atmosphere in order to perform its function as a barrier layer.
• the stack 1 can be covered with an encapsulation system 4 comprising: a first dense and insulating covering layer 2, preferably chosen from parylene, type F parylene, polyimide, epoxy resins, acrylates, fluorinated polymers, silicone, polyamide, sol-gel silica, organic silica and / or a mixture of these, deposited on the stack of notched anode and cathode notched sheets; and a second covering layer 3 composed of an electrically insulating material, deposited by depositing atomic layers on the stack of anode and cathode sheets or on said first covering layer.
• a first dense and insulating covering layer 2 preferably chosen from parylene, type F parylene, polyimide, epoxy resins, acrylates, fluorinated polymers, silicone, polyamide, sol-gel silica, organic silica and / or a mixture of these, deposited on the stack of notched anode and cathode notched sheets
• a second covering layer 3 composed of an
• This sequence can be repeated z times with z ⁇ 1. It exhibits a barrier effect, which is all the more important as the value of z is high. It is important that the last layer of the encapsulation system is a cover layer composed of an electrically insulating material so that the encapsulation system is completely sealed.
• the encapsulation system 4 consists of a simple sequence of first covering layer 2 and of second covering layer 3, while in FIG. 1, a first sequence 2a is superimposed, 3a formed by a first covering layer 2a and a second covering layer 3a, followed by a second sequence 2b, 3b of the same type.
• the first covering layer 2 is selected from the group formed by: silicones (deposited for example by impregnation or by plasma-assisted chemical vapor deposition from hexamethyldisiloxane (HMDSO)), epoxy resins, polyimide , polyamide, poly-para-xylylene (also called poly (p-xylylene), but better known under the term parylene), and / or a mixture of these.
• silicones deposited for example by impregnation or by plasma-assisted chemical vapor deposition from hexamethyldisiloxane (HMDSO)
• epoxy resins polyimide , polyamide, poly-para-xylylene (also called poly (p-xylylene), but better known under the term parylene), and / or a mixture of these.
• This first covering layer makes it possible to protect the sensitive elements of the battery from its environment.
• the thickness of said first covering layer is preferably between 0.5 ⁇ m and 3 ⁇ m.
• This first covering layer is useful above all when the electrolyte and electrode layers of the battery have porosities: it acts as a planarization layer, which also has a barrier effect.
• this first layer is capable of lining the surface of the microporosities emerging on the surface of the layer, in order to close the access thereto.
• parylene In this first covering layer 2, different variants of parylene can be used. It can be type C parylene, type D parylene, type N parylene (CAS 1633-22-3), type F parylene, or a mixture of type C parylene, D, N and / or F. Parylene is a dielectric, transparent, semi-crystalline material which exhibits high thermodynamic stability, excellent resistance to solvents and very low permeability. Parylene also has barrier properties. In the context of the present invention, type F parylene is preferred.
• This first covering layer 2 is advantageously obtained from the condensation of gaseous monomers deposited by chemical vapor deposition (CVD) on the surfaces of the stack of the battery, which makes it possible to have a conformal, thin and uniform of all the accessible surfaces of the stack.
• This first covering layer is advantageously rigid; it cannot be considered as a soft surface.
• the second covering layer 3 is composed of an electrically insulating material, preferably inorganic. It is advantageously deposited by atomic layer deposition (in English "Atomic Layer Deposition", ALD), by PECVD, by HDPCVD (in English "High Density Plasma Chemical Vapor Deposition") or by ICPCVD (Inductively Coupled Plasma Chemical Vapor Deposition in English). English) so as to obtain a conformal covering of all the accessible surfaces of the stack previously covered with the first covering layer.
• ALD atomic layer deposition
• PECVD in English "High Density Plasma Chemical Vapor Deposition”
• HDPCVD in English "High Density Plasma Chemical Vapor Deposition”
• ICPCVD Inductively Coupled Plasma Chemical Vapor Deposition in English
• the growth of the layer deposited by ALD is influenced by the nature of the substrate.
• a layer deposited by ALD on a substrate exhibiting zones of different chemical natures will have inhomogeneous growth, which may cause a loss of integrity of this protective layer. For this reason, it is useful for this second layer to rest on said first layer, which ensures a chemically homogeneous growth substrate.
• ALD deposition techniques are particularly well suited for covering surfaces with high roughness in a completely sealed and compliant manner. They make it possible to produce conformal layers, free of defects, such as holes (so-called “pinhole free” layers, ie free of holes) and represent very good barriers. Their WVTR coefficient is extremely low. The WVTR coefficient (Water Vapor Transmission Rate) is used to evaluate the water vapor permeance of the encapsulation system. The lower the WVTR coefficient, the more watertight the encapsulation system.
• this second layer is advantageously chosen as a function of the desired level of gas tightness, ie of the desired WVTR coefficient and depends on the deposition technique used, in particular among ALD, PECVD, HDPCVD and HDCVDICPCVD.
• this second layer preferably has a water vapor permeance (WVTR or WVTR coefficient) of less than 10 5 g / m 2 .d.
• WVTR water vapor permeance
• the measurement of the water vapor permeance (WVTR) can be done using a method which is the subject of US Pat. No. 7,624,621 and which is also described in the publication "Structural properties of ultraviolet cured polysilazane gas barrier layers on polymer substrates ”by A. Mortier et al., published in the journal Thin Solid Films 6 + 550 (2014) 85-89.
• Said second covering layer 3 may be of ceramic material, of vitreous material or of glass-ceramic material, for example in the form of an oxide, of the Al 2 O 3 type , of T a 2 O 5, of nitride, of phosphates, of oxynitride, or siloxane.
• This second covering layer preferably has a thickness of between 10 nm and 50 nm.
• This second cover layer 3 deposited by ALD, by PECVD, by HDPCVD (in English "High Density Plasma Chemical Vapor Deposition") or by ICPCVD (Inductively Coupled Plasma Chemical Vapor Déposition in English) on the first cover layer allows a on the one hand, to ensure the watertightness of the structure, ie to prevent the migration of water inside the object and on the other hand to protect the first covering layer, preferably of type F parylene , the atmosphere, in particular air and humidity, thermal exposures in order to avoid its degradation.
• This second covering layer thus improves the life of the encapsulated battery.
• the outer layer of the multilayer sequence of a first dense and insulating covering layer preferably chosen from parylene, type F parylene, polyimide, epoxy resins, acrylates, fluorinated polymers, silicone, polyamide and / or a mixture thereof, can be deposited on the stack of notched and notched cathode anode sheets, and of a second covering layer composed of an electrically insulating material, deposited by depositing atomic layers on said first covering layer, is necessarily a covering layer composed of an electrically insulating material deposited by depositing atomic layers in order to avoid short-circuits at the level of the contact member / encapsulation system interface.
• the stack thus coated is covered on its six faces by means of the encapsulation material.
• Contact members (electrical contacts) 8 and 8 ’ are added at the level where the cathodic, respectively anodic connection areas are visible, that is to say at the side faces 14 and 15 of the stack. These contact areas are preferably disposed on opposite sides of the battery stack to collect current (side current collectors).
• the contact members are arranged on at least the cathodic connection zone and on at least the anode connection zone, preferably on the face of the coated and cut stack comprising at least the cathode connection zone and on the face of the 'coated and cut stack comprising at least the anode connection zone.
• the contact members are formed, near the cathode and anode connection areas, of a stack of layers successively comprising a first electrical connection layer 5 ′ comprising a material charged with electrically conductive particles, preferably a resin. polymer and / or a material obtained by a sol-gel process, loaded with electrically conductive particles and even more preferably a polymeric resin loaded with graphite, and a second layer consisting of a metal foil placed on the first layer.
• a first electrical connection layer 5 ′ comprising a material charged with electrically conductive particles, preferably a resin. polymer and / or a material obtained by a sol-gel process, loaded with electrically conductive particles and even more preferably a polymeric resin loaded with graphite, and a second layer consisting of a metal foil placed on the first layer.
• the first electrical connection layer 5 5 ′ makes it possible to fix the subsequent second electrical connection layer 6 6 ′ while providing “flexibility” to the connections without breaking the electrical contact when the electrical circuit is subjected to thermal stresses and / or vibratory.
• the second electrical connection layer 6 6 ' is a metal foil.
• This second layer of electrical connection is used to permanently protect the batteries from humidity.
• metals make it possible to produce very waterproof films, more waterproof than those based on ceramics and even more waterproof than those based on polymers which are generally not very hermetic to the passage of molecules. of water. It makes it possible to increase the calendar life of the battery by reducing the WVTR at the level of the contact members.
• each first layer 5 5 ' is fixed on the terminations, respectively anodic or cathodic, by gluing.
• a layer of conductive adhesive can be used.
• these two conductive adhesives can have different physicochemical properties, in particular different wettability.
• the metal foil 6 6 ′ is fixed to the first layer 5 5 ’also by gluing, more precisely using a conductive glue which should advantageously be electrochemically stable in contact with the electrodes.
• This metal sheet glued using a conductive adhesive, improves the tightness of the terminations and reduces their electrical resistance. This technical effect is notable, whatever the manufacturing process of this sheet.
• a third electrical connection layer 7, 7 ′ comprising a conductive ink can be deposited on the second electrical connection layer 6, 6 ′; it is used to reduce WVTR, which increases battery life.
• the contact members make it possible to take up the alternately positive and negative electrical connections on each of the ends. These contact members make it possible to make the electrical connections in parallel between the different battery elements. For this, only the cathode connections come out on one end, and the anode connections are available on another end.
• the contact members 8 and 8 ' are made of a conductive material, complying with this sealing criterion.
• a conductive material is for example a conductive glass, in particular of the type charged with a metallic powder (for example charged with particles (and preferably nanoparticles) of chromium, aluminum, copper and other metals which are electrochemically stable at the potential. electrode operating mode).
• a metallic powder for example charged with particles (and preferably nanoparticles) of chromium, aluminum, copper and other metals which are electrochemically stable at the potential. electrode operating mode.
• several elementary stacks, such as the one above, can be produced simultaneously. This makes it possible to increase the efficiency of the overall process for manufacturing the batteries in accordance with the invention.
• each anode or cathode sheet comprises an active anode layer, respectively an active cathode layer.
• Each of these active layers can be solid, ie dense or porous in nature.
• an electrolyte layer or a separator impregnated with a liquid electrolyte is placed on at least one of these two sheets, in contact with the facing sheet.
• the electrolyte layer or the separator impregnated with a liquid electrolyte is interposed between two sheets of opposite polarity, ie between the anode sheet and the cathode sheet.
• FIG. 3 illustrates the stack 1100 between sheets, or anode strata 1101, as well as sheets or cathode strata 1102. As shown in this figure, cutouts are made in these different sheets, so as to produce said H-shaped empty areas, respectively anodic 1103 and cathodic 1104.
• these free zones can also have an I-shape.
• FIG. 4 illustrates the stack 1200 between anode sheets or strata 1201, as well as cathode sheets or strata 1202. As shown in this figure. 4, cutouts are made in these different sheets, so as to produce said I-shaped empty zones, respectively anodic 1203 and cathodic 1204.
• each anode and each cathode of a given battery comprises a respective main body, separated from a respective secondary body by a space free of any electrode material, of electrolyte and / or current conducting substrate.
• the empty zones can be made to have shapes that are still different from an H or an I, in particular a U shape.
• the H or I shapes are preferred.
• Said void areas can be filled with a resin during the manufacturing process.
• FIGS 5 and following illustrate further advantageous variants, in which the above battery further includes a support.
• the aforementioned support 50 which is generally flat, typically has a thickness less than 300 ⁇ m, preferably less than 100 ⁇ m.
• This support is advantageously made of an electrically conductive material, typically metallic material, in particular aluminum, copper, stainless steel which can be coated in order to improve their weldability property with a thin layer of gold, nickel and tin.
• the so-called front face of the support, which faces towards the elementary stack, and 52 are denoted respectively by the opposite rear face.
• This support is perforated, that is to say that it comprises spaces 53 and 54 delimiting a central sole 55 as well as two opposite side bands 56 and 57.
• the different regions 55, 56 and 57 of this support are, consequently, mutually isolated on the electrical plan.
• the side bands 56 and 57 form mutually electrically isolated regions, which are capable of being connected with contact members belonging to the battery.
• the electrical insulation is achieved by leaving empty spaces 53 and 54 which, as will be seen below, are filled with a stiffening material.
• the support and the stack are mutually secured by a layer 60.
• the latter is typically formed by means of a non-conductive adhesive, in particular of the epoxy or acrylate type.
• the thickness of this layer 60 is typically between 5 ⁇ m and 100 ⁇ m, in particular close to 50 ⁇ m.
• this layer at least partially covers the spaces 53 and 54 above, so as to mutually isolate the anodic and cathodic contact members as will be detailed below.
• pads 30 and 31 of a conductive adhesive make it possible to fix the contact members on the support 5, while ensuring electrical continuity.
• the material constituting the contact members 8 and 8 ' is capable of ensuring a sealing function according to the above criterion.
• this material typically belongs to the list presented above, with reference to the description of the first three figures.
• the elementary stack of anodes and cathodes is protected against the entry of potentially harmful gases.
• the material constituting the contact members 8 and 8 ' is not waterproof, within the meaning of the invention.
• the battery advantageously comprises a so-called additional encapsulation layer 45, illustrated in solid lines in FIG. 6.
• This additional layer makes it possible to confer the desired seal on the stack, so that the latter is the object of a "re-encapsulation".
• this layer 45 has a water vapor permeance (WVTR or WVTR coefficient) of less than 10 -5 g / m 2 .d, as defined above.
• this encapsulation layer 45 first of all covers the contact members 8 and 8 ’. Furthermore, it extends in the intermediate space formed between the initial encapsulation layer 41 and the face facing the support 50. Finally, it also extends in the free spaces 53 and 54 of the support. On the lower part of this FIG. 6, the reference 45 has also been placed three more times, on these specific areas. Therefore, components harmful to the proper functioning of the battery cannot access the elementary stack of anodes and cathodes. In other words, the invention makes it possible to avoid any potential “gateway” for these harmful components.
• the elementary stack is placed first on the support, with the interposition of the layer of non-conductive adhesive. Then the side faces of the stack are covered by means of the contact members.
• the contact members it is also possible to place, on its support, the elementary stack already provided with these contact members, but on the other hand without its encapsulation system. Finally, the encapsulation system is removed, taking care to guarantee the overall seal, as described above.
• the battery is also equipped with a stiffening system.
• the latter can first of all be applied to the battery according to FIG. 5, having sealed contact members.
• This stiffening system is then assigned the reference 80 as a whole.
• the stiffening material covers the upper face of the battery, as well as the lateral contact members.
• This stiffening material also advantageously fills the intermediate space located between the layer 41 and the support 50, as well as the free spaces 5354 of the support.
• the reference 80 has been worn several times in the various zones occupied by the stiffening material.
• the stiffening material can also be applied to the battery of FIG. 6, having contact members which are not waterproof.
• the stiffening material covers the additional encapsulation system 45, at its upper and lateral edges. It should be noted that this stiffening material can be intimately linked to the encapsulation material 45, in the free spaces 53 54, as well as in the intermediate space between the layer 41 and the support 50.
• This stiffening system 80 can be made of any material, making it possible to ensure this function of mechanical stiffness.
• a resin which may consist of a simple polymer or a polymer loaded with inorganic fillers will be chosen.
• the polymer matrix may be of the family of epoxies, acrylates, fluoropolymers for example, the fillers possibly consisting of particles, flakes or glass fibers.
• this stiffening system 80 can provide an additional barrier function with regard to humidity.
• a glass with a low melting point will be chosen, for example, thus ensuring mechanical resistance and an additional barrier to humidity.
• This glass can, for example, be of the SiO 2 - B 2 O 3 family ; Bi 2 O 3 - B 2 O 3 , ZnO- Bi 2 O 3 -B 2 O 3 , TeO 2 -V 2 O 5 , PbO-SiO 2 .
• the stiffening system 80 has a much greater thickness than that of the encapsulation system.
• E80 denotes the smallest thickness of this stiffening system, at the level of the covering of the front face of the stack.
• this thickness E80 is between 20 and 250 ⁇ m, typically close to 100 ⁇ m.
• This stiffening system thus provides a mechanical and chemical protection function, possibly associated with an additional gas barrier function.
• the integration of the battery according to the invention on the support 50, as described above, can be carried out by individually placing each elementary stack on its support. Nevertheless, advantageously, it is preferred to simultaneously manufacture a plurality of batteries, each incorporating such a support.
• FIGS. 7 to 9 such a simultaneous manufacturing method is illustrated in FIGS. 7 to 9.
• a support frame 105 is advantageously used, which is intended to form a plurality of supports 50.
• This frame 104 which is shown on a large scale in FIG. 7, has a peripheral edge 150, as well as a plurality of blanks 151, each of which allows the manufacture of a respective battery.
• Each blank comprises a central area 155, intended to form the sole 55, as well as two side blocks 156 and 157 intended to form the bands 56 and 57 respectively.
• the area and the blocks are mutually separated by slots 153 and 154, which are intended to form the spaces 53 and 54.
• the different blanks are immobilized, both with respect to each other, as well as with respect to the peripheral edge, by means of different respectively horizontal 158 and vertical 159 rods.
• each blank 151 receives an already encapsulated battery which therefore conforms to the representation of FIG. 1.
• a dose 106 of non-conductive adhesive is deposited on each pad 155, intended to form the layer 6, as well as doses 130 and 131 of conductive adhesive, intended to form the pads 30 and 31.
• the encapsulated stack is then brought into contact with the support, so as to form the layer of adhesive 60 as well as the pads 30 and 31, making it possible to mutually fix this stack with respect to this support.
• FIG. 9 a cutout is made of the frame 150, on which the various constituents of the plurality of batteries have been placed.
• the different cutting lines are shown in dotted lines, being assigned references D for the cuts according to the longitudinal dimension of the batteries and references D 'for the cuts according to their lateral dimension. Note that, depending on the two dimensions of the frame, some areas R and R ’are intended to be discarded.
• the electrochemical device according to the invention can include one or more additional electronic components.
• a component can for example be of the LDO type (which means in English “Low Dropout Regulator”, namely a regulator with low voltage drop).
• LDO Low Dropout Regulator
• RTC module which means in English “Real Time Clock”, namely a clock function
• an energy recovery module in English “Energy Harvesting”
• the electronic component (s) are advantageously covered by the same encapsulation system as that protecting the elementary stack.
• this energy consumption device is shown schematically, being assigned the reference 1000. It comprises a body 1002, on which the lower face of the support rests. The mutual fixing between this body 1002 and the support 50 is carried out by any suitable means. It will be noted that, in this FIG. 10, the device 1000 integrates the battery of FIG. 5, the contact members of which are sealed. As a variant not shown, it is also possible to combine the battery of FIG. 6 with the energy consumption device 1000. In this case, as explained above, it should be ensured that the complementary encapsulation material 45 guarantees perfect sealing with respect to the elementary stack of anodes and cathodes. In this connection, reference will be made to the description given above, in particular with regard to the various locations of the reference number 45 in this FIG. 6.
• the device 1000 further comprises an energy consuming element 1004, as well as connection lines 1006 1007 electrically connecting the regions 56 57 of the support 50 with this element 1004.
• the control can be provided by a component of the battery itself, and / or by a component (not shown) belonging to the device 1000.
• an energy consumption device can be an electronic circuit of amplifier type, an electronic circuit of clock type (such as a component.
• RTC Real Time Clock
• an electronic circuit of the volatile memory type an electronic circuit of the static random access memory (SRAM, Static Random Access Memory), an electronic circuit of the microprocessor type, an electronic circuit of the watchdog type (watchdog timer ), a component of the liquid crystal display type, a component type LED (Light Emitting Diode), an electronic circuit of the voltage regulator type (such as a low-drop voltage regulator circuit, abbreviated LDO, Low-dropout regulator), an electronic component of the CPU (Central Processing Unit) type .
• SRAM static random access memory
• microprocessor type an electronic circuit of the watchdog type (watchdog timer )
• a component of the liquid crystal display type such as a low-drop voltage regulator circuit, abbreviated LDO, Low-dropout regulator
• an electronic component of the CPU Central Processing Unit
• the conductive support 750 is multilayer, as opposed to the support 50 above, of the monolayer type. Furthermore, this support 750 is of the solid type, as opposed in particular to the above metal grid which is of the perforated type. As shown in this FIG. 11, the support 750 is formed of layers, made for example of a polymer material. These layers extend one below the other, their main plane being substantially parallel to the plane of the layers forming the stack 1 above. The structure of this support is therefore to be compared to that of a printed circuit (in English "Printed Circuit Board” or PCB).
• This layer 756 which is mainly formed by a polymer material, such as epoxy resin, is provided with two inserts 757.
• the latter which are made of a conductive material, in particular metallic, are intended to cooperate with the respectively anode contacts. and cathode of the battery. It will be noted that these inserts 757 are mutually isolated, thanks to the epoxy resin of the layer 756.
• a layer 758 also made of a polymeric material such as an epoxy resin.
• This layer 758 is provided with 2 inserts 759, made of conductive material, which are brought into electrical contact with the first inserts 757. As for the layer 756, these inserts 759 are mutually insulated.
• this layer 760 is formed of a conductive material, typically similar to that constituting the inserts 757 and 759 above.
• This layer is equipped with two annular inserts 761, which are made of an insulating material, in particular an epoxy resin as above. These inserts 761 receive, in their hollow central part, discs 762 of conductive material, which are placed in contact with adjacent conductive inserts 759. It will be noted that these conductive discs 762 are mutually insulated, by means of the rings 761.
• layers 764 and 766 lower in FIGS. 11 and 12, which are respectively identical to the layers 758 and 756 above.
• the layer 764 is equipped with 2 inserts 765, in contact with the discs 762, while the lower layer 766 is provided with 2 inserts 767, in contact with the above inserts 765.
• the various conductive inserts 757,759,762,765 and 767 define paths conductors denoted 753 754, which allow the opposite end faces of the support 705 to be electrically connected. These paths are mutually insulated, either by the layers 756,758,764 and 766, or by the discs 761.
• the stiffening system may be different from that 80 of the first embodiment.
• a protective film 780 by means of a lamination step.
• a film which has barrier properties, is for example made of polyethylene terephthalate (PET) incorporating inorganic multilayers; such a product, which may be suitable for this application, is commercially available from the company 3M under the reference Ultra Barrier Film 510 or Ultra Barrier Solar Films 510-F.
• PET polyethylene terephthalate
• Such a stiffening system, using films obtained by lamination can however find other applications, in addition to those of FIG. 11.
• FIG. 11 also illustrates the integration, on an energy consuming device 1000, of the support 705, of the stack 702, of the conductive pads 730 and 740, of the encapsulation 707 and of the film 708.
• the energy produced at the level of the stack 702 is transmitted, by the contact members 730 and 740, at the level of the upper inserts 757. Then this energy is transmitted, along the connection paths 753 754 described below. above, to the power consumption device 1000.
• the multilayer support can be formed only of two distinct layers, one below the other. These layers define conductive paths, analogous to those 753,754 described above.
• This particular embodiment, illustrated with reference to FIG. 11, has specific advantages. Indeed, the multilayer support such as that 750 has a very low thickness, advantageously less than 100 ⁇ m. Moreover, such a support has a certain flexibility, so that it can accompany slight changes in the dimensions of the battery, called “breaths” in the introductory part of the present description. This support also benefits from particularly satisfactory bending resistance, with a view to its integration into a flexible electronic circuit. The invention is not limited to the examples described and shown.
• each current-collecting substrate prefferably perforated, ie to have at least one through opening.
• the transverse dimension of each perforation (or opening) is between 0.02 mm and 1 mm.
• the void rate of each perforated substrate is between 10% and 30%. This means that, for a given area of this substrate, between 10% and 30% of this area is occupied by the perforations.
• the technical function of these perforations or openings is as follows: the first layer deposited on one of the two sides of the substrate will stick, inside the openings, against the first layer deposited on the other of the two sides of the substrate .
• This improves the quality of the deposits, in particular the adhesion of the layers located in contact with the substrate.
• the aforementioned layers undergo a slight shrinkage, namely a slight reduction in their longitudinal and lateral dimension, while the dimensions of the substrate are substantially invariable. This tends to create shear stresses at the level of the interface between the substrate and each layer, which thus affects the quality of the adhesion; this stress increases with the thickness of the layers.
• the process according to the invention is very particularly suitable for the manufacture of entirely solid batteries, i.e. batteries in which the electrodes and the electrolyte are solid and do not include a liquid phase, even impregnated in the solid phase.
• the method according to the invention is also very particularly suitable for the manufacture of batteries considered to be quasi-solid comprising at least one separator impregnated with an electrolyte.
• Said separator is preferably a porous inorganic layer exhibiting: a porosity, preferably a mesoporous porosity, greater than 30%, preferably between 35% and 50%, and even more preferably between 40% and 50%, pores with a mean diameter D50 less than 50 nm.
• the separator is often understood to be interposed between the electrodes. In the present exemplary embodiment, it is a ceramic or glass-ceramic filter deposited on at least one of the electrodes, and sintered to achieve the solid assembly of the batteries. The fact that a liquid is nano-confined inside this separator confers quasi-solid properties on the final battery.
• the thickness of the separator is advantageously less than 10 ⁇ m, and preferably between 3 ⁇ m and 16 ⁇ m, preferably between 3 ⁇ m and 6 ⁇ m, more preferably between 2.5 ⁇ m and 4.5 ⁇ m, so as to reduce the final thickness of the battery without reducing its properties.
• the pores of the separator are impregnated with an electrolyte, preferably with a phase carrying lithium ions such as liquid electrolytes or an ionic liquid containing lithium salts.
• the “nanoconfined” or “nanopiégé” liquid in the porosities, and in particular in the mesoporosities, can no longer come out.
• the method according to the invention, and the encapsulation system can in particular be applied to any type of thin film battery, in particular to any type of lithium ion battery.
• These lithium ion batteries can be all-solid multilayer lithium ion batteries, quasi-solid multilayer lithium ion batteries and can in particular be all-solid multilayer lithium ion microbatteries. More generally, these lithium ion batteries can in particular use anode layers, electrolyte layers and cathode layers such as those described in document WO 2013/064777 in the context of a microbattery, namely anode layers made from one or more of the materials described in claim 13 hereof, cathode layers made from one or more of the materials described in claim 14 hereof, and electrolyte layers made from one or more of the materials described in claim 15 herein.
• the battery according to the invention can be a lithium ion microbattery, a lithium ion mini battery, or even a high power lithium ion battery.
• it can be designed and dimensioned so as to have a capacity less than or equal to approximately 1 mA h (commonly called a “microbattery”), so as to have a power greater than approximately 1 mA h up to approximately 1 A h ( commonly called “mini-battery”), or even so as to have a capacity greater than about 1 A h (commonly called a "power battery”).
• microbatteries are designed to be compatible with microelectronics manufacturing processes.
• the batteries of each of these three power ranges can be produced: either with layers of the “all solid” type, ie devoid of impregnated liquid or pasty phases (said liquid or pasty phases possibly being a conductive medium of lithium ions, capable of acting as an electrolyte), either with mesoporous “all solid” type layers, impregnated with a liquid or pasty phase, typically a conductive medium of lithium ions, which spontaneously enters the interior of the layer and which no longer emerges from this layer, so that this layer can be considered as quasi-solid, either with impregnated porous layers (ie layers having a network of open pores which can be impregnated with a liquid or pasty phase, and which gives these layers have wet properties).
• layers of the “all solid” type ie devoid of impregnated liquid or pasty phases (said liquid or pasty phases possibly being a conductive medium of lithium ions, capable of acting as an electrolyte)
• Li 4 Ti 5 O 12 nanoparticles were prepared as the anode material by grinding so as to obtain a particle size of less than 100 nm.
• the Li 4 Ti 5 O 12 nanoparticles were then dispersed in absolute ethanol at 10 g / l with a few ⁇ m of citric acid in order to obtain a suspension of Li 4 Ti 5 O 12 nanoparticles.
• the negative electrodes were prepared by electrophoretic deposition of the Li 4 Ti 5 O 12 nanoparticles contained in the suspension prepared beforehand, on stainless steel strips.
• the Li 4 Ti 5 O 12 film (approximately 1 ⁇ m) was deposited on both sides of the substrate. These films were then heat treated at 600 ° C. for 1 hour in order to weld the nanoparticles together, to improve adhesion to the substrate and to perfect the recrystallization of Li 4 Ti 5 O 12 .
• the thin film of Li 1 + x Mn 2-y O 4 (approximately 1 ⁇ m) was deposited on both sides of the substrate. These films were then heat treated at 600 ° C. for 1 hour in order to weld the nanoparticles together, to improve adhesion to the substrate and to perfect the recrystallization of Li 1 + x Mn 2-y O 4 .
• a suspension of Li 3 PO 4 nanoparticles was prepared from the two solutions presented below.
• solution B 16.24 g of H 3 PO 4 (85 wt% in water) were diluted in 422.4 ml of water, then 182.4 ml of ethanol was added to this solution in order to obtain a second solution hereinafter called solution B.
• Solution B was then added, under stirring vacuum, to solution A.
• the reaction medium was homogenized for 5 minutes then was kept for 10 minutes with magnetic stirring. It was allowed to settle for 1 to 2 hours. The supernatant was discarded and then the remaining suspension was centrifuged for 10 minutes at 6000 g. Then 1.2 l of water were added to resuspend the precipitate (use of a sonotrode, magnetic stirring). Two additional washes of this type were then carried out with ethanol. With vigorous stirring, 15 ml of a solution of Bis (2- (methacryloyoloxy) ethyl) phosphate at 1 g / ml were added to the colloidal suspension in ethanol thus obtained. The suspension has thus become more stable. The suspension was then sonicated using a sonotrode.
• the suspension was then centrifuged for 10 minutes at 6000 g.
• the pellet was then redispersed in 1.2 l of ethanol and then centrifuged for 10 minutes at 6000 g.
• the pellets thus obtained are redispersed in 900 ml of ethanol in order to obtain a 15 g / l suspension suitable for carrying out an electrophoretic deposit.
• Agglomerates of about 200 nm consisting of primary Li 3 PO 4 particles of 10 nm were thus obtained in suspension in ethanol.
• Thin porous Li 3 PO 4 layers were then deposited by electrophoresis on the surface of the anodes and cathodes previously produced by applying an electric field of 20V / cm to the suspension of Li3PO4 nanoparticles previously obtained, for 90 seconds to obtain a layer approximately 2 ⁇ m.
• the layer was then dried in air at 120 ° C. and then a calcination treatment at 350 ° C. for 120 minutes was carried out on this previously dried layer in order to remove all traces of organic residues.
• the stack was placed under a pressure of 5 MPa and then dried under vacuum for 30 minutes at 10-3 bars.
• the press platens were then heated to 550 ° C with a rate of 0.4 ° C / second.
• the stack was then thermo-compressed under a pressure of 45 MPa for 20 minutes, then the system was cooled to room temperature.
• a first layer of parylene F (CAS 1785-64-4) about 2 ⁇ m thick was deposited by CVD on the electrochemical cell, respectively on the battery comprising several electrochemical cells.
• a layer of Al 2 O 3 alumina was then deposited by ALD on this first layer of parylene F.
• the electrochemical cell respectively the battery comprising several electrochemical cells coated with a layer of parylene was introduced into the chamber of a ALD P300 Picosun TM reactor.
• the chamber of the ALD reactor was previously placed under vacuum at 5 hPa and at 120 ° C and previously subjected for 30 minutes to a flow of trimethylaluminum (hereafter TMA, CAS No: 75-24-1), a chemical precursor.
• TMA trimethylaluminum
• a 30 nm Al2O3 layer was deposited by ALD.
• a layer of parylene F approximately 2 ⁇ m thick was then deposited by CVD on the second layer of Al 2 O 3 alumina.
• a layer of Al 2 O 3 alumina approximately 30 nm thick was then deposited by ALD, as indicated above, on this third layer of parylene F.
• the stack thus encapsulated was then cut according to section planes making it possible to obtain an electrochemical cell, respectively a unit battery, with the exposure on each of the section planes of the cathode current collectors, respectively anode of the electrochemical cell. respectively of the battery.
• the encapsulated stack has thus been cut out on two of the six faces of the stack so as to make the cathode current collectors, respectively anode, visible.
• PYR14TFSI is the common abbreviation of 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide.
• LITFSI is the common abbreviation for lithium bis-trifluoromethanesulfonimide (CAS RN 90076-65-6).
• the ionic liquid comes in instantly by capillarity in the porosities. Each of the two ends of the system was kept immersed for 5 minutes in a drop of the electrolyte mixture.
• a conductive resin charged with carbon of the Dycotec DM-Cap-4701S type is applied to the ends of the electrochemical cell, respectively of the battery, encapsulated and cut.
• a sheet of stainless steel type 316L 5 ⁇ m thick is applied on this thin layer of conductive resin. Keeping the small sheet of stainless steel in contact by pressure on the end of the battery, the resin is dried at 100 ° C. for 5 minutes.
• a second termination layer is then made at both ends of the battery. This second layer covers the stainless steel sheets glued to each end.
• This second layer is obtained by immersing the ends in a conductive glue charged with silver.
• the components are then barrel-treated in a first bath of nickel sulfamate acidified with boric acid at 60 ° C for 25 minutes under a current of 6 A. After rinsing, a deposit of tin is made on the nickel deposit. in order to ensure the weldability of the component.
• This deposition is also carried out in a barrel by electrolytic deposition in a bath of tin metasulfonate and boric acid at pH 4 at 25 ° C. for 35 minutes.

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• 2020
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