Classifications

• • 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
  • 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
  • H01M10/04—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
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • 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
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—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
  • 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
  • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
• • 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
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic 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
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
• • 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
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
  • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
• • 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
  • H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
  • H01M50/529—Intercell connections through partitions, e.g. in a battery 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
  • H01M50/50—Current conducting connections for cells or batteries
  • H01M50/531—Electrode connections inside a battery casing
  • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
• • 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
• • 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 the manufacture of batteries. It can be applied in particular to lithium ion batteries.
• the invention relates to a new method for manufacturing batteries, and in particular lithium ion batteries. It also relates to the batteries obtained by this process, which have a new architecture which gives them an improved lifespan.
• WO 2016/001584 describes sheets comprising a conductive substrate successively covered with an electrode layer covered with an electrolyte layer; these sheets are cut, before or after deposition, according to patterns, in particular in the shape of a U. These sheets are stacked in an alternating manner so as to constitute a stack of several elementary cells.
• the cutout patterns of the anodes and cathodes are placed in a "head to tail" configuration so that the stack of cathode and anode layers is offset laterally.
• an encapsulation system in a thick layer of ten microns and conformai, typically a polymeric layer, on the stack and in the available cavities present within of stacking. This ensures on the one hand, the rigidity of the structure at the cutting planes and on the other hand, the protection of the battery cell from the atmosphere.
• FIG. 12 illustrates a structure of a lithium ion battery described in WO 2016/001584.
• the battery 200 comprises several anodes 230 and several cathodes 210, which are arranged one below the other alternately.
• Each anode and each cathode comprises a layer of a respective active anode or cathode material, called anode layer, respectively cathode layer.
• a layer of an electrolyte material is interposed between the anode and the cathode, so that this electrolyte material separates two active layers opposite.
• the thickness of the various layers which constitute them normally does not exceed 10 ⁇ m, and is often between 1 ⁇ m and 4 ⁇ m.
• the battery has, on a first lateral edge 201, anode connections 230 'located one below the other. Furthermore, on the opposite lateral edge 202, cathode connections 210 ′ are provided, located one below the other. The stack of anodes 230 and cathodes 210 is offset laterally. The cathode connections 210 'are located projecting from the free face 230 ”of the anode. Similarly, on the opposite edge 201, the free face 210 "of the cathode is set back with respect to the free face of the anode on which anode connections 230 'are subsequently deposited.
• the present invention aims to remedy at least in part certain drawbacks of the prior art mentioned above.
• It aims in particular to propose a process which reduces the risk of short circuit, and which makes it possible to manufacture a battery having a low self-discharge.
• It aims in particular to propose a method which makes it possible to manufacture in a simple, reliable and rapid manner a battery having a very long lifespan.
• the present invention provides as a first object a battery comprising at least one anode and at least one cathode, arranged one above the other in an alternating manner, said battery comprising lateral edges comprising an anodic connection zone and a zone cathodic connection, preferably laterally opposite the anodic connection zone, and longitudinal edges, in which the anode comprises
• the cathode includes
• a current collector substrate at least one cathode layer, and
• each anode and each cathode comprises a respective main body, and a respective secondary body, said main bodies and secondary bodies being separated by a free space of any material of electrode, electrolyte and / or current collector substrate, said free space connecting the opposite longitudinal edges of the battery, ie said free space extending between the opposite longitudinal edges of the battery.
• the present invention provides as a second object a battery comprising at least one anode and at least one cathode, arranged one above the other in an alternating manner, said battery comprising lateral edges comprising an anode connection zone and a zone cathodic connection, preferably laterally opposite the anodic connection zone, and longitudinal edges, in which the anode comprises a current collector substrate,
• the cathode includes
• each anode and each cathode comprises a respective main body, separated from a respective secondary body, by a free space of any electrode material , electrolyte and / or current collector substrate, said free space connecting the opposite longitudinal edges of the battery, ie said free space extending between the opposite longitudinal edges of the battery.
• the battery comprises an encapsulation system completely covering four of the six faces of said battery, the two remaining faces comprising an anodic connection zone and a cathodic connection zone.
• the encapsulation system includes:
• At least one first covering layer preferably chosen from parylene, type F parylene, polyimide, epoxy resins, silicone, polyamide, sol-gel silica, organic silica and / or a mixture of these, deposited on the battery,
• At least a second covering layer composed of an electrically insulating material, deposited by depositing atomic layers on said at least first covering layer, it being understood that this sequence of at least a first covering layer and at least one second covering layer can be repeated z times with z 3 1.
• the anodic connection area and the cathodic connection area are covered by a termination system.
• the termination system successively comprises: a first layer of a material loaded with graphite, preferably based on epoxy resin loaded with graphite,
• the width of the free space is between 0.01 mm and 0.5 mm.
• the width of the secondary bodies is between 0.05 mm and 2 mm.
• the free spaces of the cathodes are superimposed.
• the free spaces of the anodes are superimposed.
• Another object of the invention is a method of manufacturing a battery, said battery comprising at least one anode and at least one cathode, arranged one above the other in an alternating manner, said battery comprising edges longitudinal and side edges, in which the anode comprises
• the cathode includes
• each anode comprising an anodic connection zone, situated in the vicinity of a first lateral edge of the battery, while each cathode comprises a cathodic connection zone, situated on a second lateral edge of the battery, opposite to said first edge
• said manufacturing method comprising: a) supplying a stack of alternating sheets, this stack comprising first sheets or sheets of anode each of which is intended to form an anode layer of several batteries, as well as second sheets or cathode sheets, each of which is intended to form a cathode layer of several batteries, each anode sheet comprising at least s an anode slot and each cathode sheet comprising at least one cathode slot,
• the cut-out stack is encapsulated, by depositing: at least one first covering layer, preferably chosen from parylene; type F parylene, polyimide, epoxy resins, silicone, polyamide, sol-gel silica, organic silica and / or a mixture thereof, on the battery, and then
• At least one second covering layer composed of an electrically insulating material, deposited by depositing atomic layers on said at least first covering layer, it being understood that the sequence of at least one first covering layer and at least a second covering layer can be repeated z times with z> 1.
• the impregnation of the cut and encapsulated stack is carried out with a phase carrying lithium ions such as liquid electrolytes or an ionic liquid containing lithium salts.
• the ends of the battery are produced by successively depositing a first layer of a material loaded with graphite, preferably based on epoxy resin loaded with graphite,
• the two cuts are made through at least a majority of the anodes and cathodes, in particular through all of the anodes and cathodes.
• the distances between each cut and the opposite ends of the longitudinal parts are identical.
• its distances are between 0.05 mm and 2 mm.
• each slot has an overall shape of H, the longitudinal parts forming the main vertical recesses of the H, while the lateral part forms the channel of the H.
• each lateral part of the slots delimits a free space of any electrode, electrolyte and / or current-collecting substrate material connecting or extending between the opposite longitudinal edges of the battery, said free space separating, for each anode and each cathode, a main body of a secondary body.
• the width of the lateral part of the slots is between 0.05 mm and 2 mm.
• each sheet belonging to said stack comprises several slit lines arranged one next to the other.
• the two cuts are made through all of the slots of the same line.
• each sheet comprises several rows of slots arranged one below the other.
• the distance separating adjacent cutouts, formed in adjacent lines is between 0.05 mm and 5 mm.
• the number of lines is between 10 and 500, while the number of rows is between 10 and 500.
• each cutting is carried out by a sawing process, by a dicing process, by guillotine, or by laser.
• FIG. 12 represents a battery according to the state of the art.
• FIG. 1 is a perspective view of the anode and cathode sheets intended to form a stack according to the method of manufacturing batteries according to the invention.
• FIG. 2 is a front view, illustrating one of the sheets of FIG. 1.
• FIG. 3 is a front view, on a larger scale, illustrating H-shaped slots formed in adjacent sheets.
• FIG. 4 ⁇ is a perspective view, also on a large scale, illustrating these H-shaped slots made in adjacent sheets.
• FIG. 5 is a top view, illustrating a cutting step carried out on different slots provided in the stack of the preceding figures.
• FIG. 6 is a top view, illustrating on a larger scale the cutouts formed on an H-shaped slot.
• FIG. 7 is a sectional view along the line VII-VII indicated in FIG. 6.
• FIG. 8 is a sectional view along the line VIII-VIII indicated in FIG. 6.
• FIG. 9 is a top view illustrating a battery according to the invention, which is capable of being obtained in particular according to the method of the preceding figures.
• FIG. 10 is a front view illustrating a battery according to the invention, which is capable of being obtained in particular according to the method of the preceding figures.
• FIG. 1 1 is a perspective view illustrating a battery according to the invention, which can be obtained in particular according to the method of the preceding figures.
• FIG. 12 is a perspective view illustrating a battery according to the prior art.
• FIG. 13 is a top view, illustrating a cutting step carried out on various H-shaped slots formed on an anode or cathode sheet according to a second variant of the invention.
• FIG. 14 is a top view, illustrating on a larger scale the cutouts made on H-shaped slots according to the second variant of the invention.
• FIG. 15 is a perspective view illustrating a battery according to the invention, which can be obtained in particular according to the second variant of the invention.
• the method according to the invention firstly comprises a step in which a stack I of alternate sheets is produced, these sheets being called in the following, as the case may be, "anode sheets” and "Cathode sheets".
• each anode sheet is intended to form the anode of several batteries
• each cathode sheet is intended to form the cathode of several batteries.
• this stack is formed by a higher number of sheets, typically between ten and one thousand.
• all these sheets have perforations 2 at their four ends so that when these perforations 2 are superimposed, all the cathodes and all the anodes of these sheets are arranged specifically, as will be explained in addition great detail below (see Figures 1 and 2).
• These perforations 2 at the four ends of the sheets can be produced by any suitable means, in particular on anode and cathode sheets after manufacture or on anode and / or cathode sheets coated with an electrolyte layer or coated a separator so that this electrolyte layer or this separator is interposed between two sheets of opposite polarity, ie between the anode sheet and the cathode sheet.
• each anode or cathode sheet comprises an active anode layer, respectively an active cathode layer.
• Each of these active layers can be solid, i.e. 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, i.e. between the anode sheet and the cathode sheet.
• the cathode sheets 1 have an identical structure.
• the anode sheets 3 have a structure very similar to that of the cathode sheets 1.
• the cathode sheet 1 has a quadrilateral shape, substantially of the square type. It delimits a central zone 10 called perforated, in which are formed H-shaped slots which will be described below. With reference to the positioning of these H-shaped slots, a so-called vertical direction YY of the sheet is defined, which corresponds to the vertical direction of these H, as well as a so-called horizontal direction XX of the sheet, perpendicular to the direction YY. .
• the central zone 10 is bordered by a peripheral frame 12 which is solid, that is to say devoid of slots. The function of this framework is in particular to ensure easy handling of each sheet.
• the H-shaped slots are distributed along lines Li to L y , arranged one below the other, as well as in rows Ri to R x provided one next to the other.
• the anode and cathode sheets used can be plates of 100 mm x 100 mm .
• the number of lines of these sheets is between 10 and 500, while the number of rows is between 10 and 500.
• its dimensions may vary and the number of lines and rows by anode and cathode sheets can be adapted accordingly.
• the dimensions of the anode and cathode sheets used can be adjusted as required.
• the slots 14 are through, that is to say that they open on the respectively upper and lower faces of the sheet.
• the slots 14 can be produced in a manner known per se, directly on the substrate, before any deposition of anode or cathode materials by chemical etching, by electroforming, by laser cutting, by microperforation or by stamping.
• These slots can also be produced on substrates coated with anode or cathode materials, on anode or cathode sheets coated with an electrolyte layer or a separator, in a manner known per se, for example by laser cutting, by femtosecond laser cutting, by microperforation or by stamping.
• the slots 14, produced in all of the cathodes, are superimposed as shown in particular in FIG. 3.
• the slot 14 is formed by two vertical and parallel main recesses 16, which are connected in their upper part by a horizontal channel 18, preferably perpendicular to the two vertical main recesses 16.
• each anode is also provided with different lines and rows of slots 34, provided in the same number as the slots 14.
• the structure of each slot 34 is substantially similar to that of each slot 14, namely that this slot 34 comprises two vertical main recesses 36, connected by a channel 38.
• the dimensions of the vertical main recesses 36 are identical to those vertical main recesses 16 and, similarly, the dimensions of the channels 38 are similar to those of the channels 18.
• the main vertical recesses 36 are superimposed with those 16.
• the channels 18 and 38 are mutually symmetrical in top view, with respect to the median axis of the H, which is denoted XH.
• each cut is made between a respective channel and the opposite end of H. It is assumed that we neglect the thickness of said cut. Under these conditions, with reference to this FIG. 6, by way of nonlimiting examples, we note:
• the distance D20 between the cut D n and the opposite face of the horizontal channel 18 is between 0.05 mm and 2 mm, it being understood that this distance D20 is less than or equal to Die;
• each final battery is delimited, at the top and at the bottom, by the two cutouts and, to the right and to the left, by the interior faces of the main vertical recesses of the H.
• we have hatched the batteries 100 once cut by the cutting lines D n and D ' n the areas have been illustrated with dots 40 of the sheets of the stack, which do not form the batteries, while the volume of the slots is left blank.
• Figures 7 and 8 are sectional views, taken along parallel section lines. Section VII-VII extends through the main vertical recesses of the H, while section VIII-VIII crosses the material.
• the areas 40 also illustrated in FIG. 5, have been referenced, which correspond to falls of material, in particular falls of anode materials 43 and cathode materials 41.
• FIG. 7 the areas 40, also illustrated in FIG. 5, have been referenced, which correspond to falls of material, in particular falls of anode materials 43 and cathode materials 41.
• the cuts are made both through anodes and cathodes, namely at a distance D 2 o from the channels of the H-shaped slots so as to have for each cathode 1, respectively each anode 3 of the battery 100 a main body 111, respectively 131, separated from a secondary body 112, respectively 132, by a free space of any electrode material, electrolyte and / or current-collecting substrate 113, respectively 133.
• Application WO 2016/001584 describes stacks of several elementary cells, consisting of anode sheets and of cathode stacked alternately and offset laterally (cf. FIG. 12), encapsulated in an encapsulation system to ensure protection of the battery cell vis-à-vis the atmosphere.
• the cutting of these encapsulated stacks making it possible to obtain unitary batteries, with anodic and cathodic connections exposed, is carried out according to a cutting plane crossing an alternating succession of electrode and encapsulation system. Due to the difference in density existing between the electrode and the battery encapsulation system of the prior art, the cutting carried out according to this cutting plane induces a risk of tearing of the encapsulation system around the plane of cut, and thus the creation of short circuits.
• the encapsulation layer fills the interstices of the stack of sheets carrying U-shaped cutouts.
• This encapsulation layer introduced at these interstices is thick and does not ' does not adhere very well to the stack, inducing this risk of tearing off the encapsulation system during subsequent cutting.
• this risk is eliminated with the use of sheets carrying H-shaped cutouts, because the heat-pressed H-shaped mechanical structure is extremely rigid around the cutout, due to the alternating superposition of sheets of cathode and anode.
• the use of such a rigid structure, with the use of sheets carrying H-shaped cutouts, makes it possible to reduce the number of defects during cuts, increase the cutting speed and thus improve battery production efficiency.
• the cuts D ′ n and D n are made through anodes and cathodes of comparable density inducing a clean cut of better quality.
• the presence of a free space of any electrode material, electrolyte and / or current-collecting substrate prevents any risk of short circuit.
• X100 and Y100 denote the median axes respectively longitudinal and lateral of this battery. There are 101 and 102 the side edges, 103 and 104 the longitudinal edges of this battery. We also note 110 each cathode, and 130 each anode. The number of these cathodes, which is identical to the number of these anodes, corresponds to the number of cathode sheets and anode sheets of the above stack.
• the free space (1 13) connects the opposite longitudinal edges of the battery which are shown as upper and lower in FIG. 9. This free space extends between the opposite longitudinal edges of the separating battery, for each anode and each cathode , a main body of a secondary body.
• Each cathode 110 comprises a main body 111, a secondary body 112 situated on a first lateral edge 101, as well as a space free of any electrode material, electrolyte and / or current-collecting substrate 113.
• the latter whose width corresponds to that of the channel 18 of the slot 14 described above, extends between the longitudinal edges 103 and 104.
• each anode 130 comprises a main body 131, as well as a secondary body 132 located on the lateral edge 102, opposite that 101.
• the main body 131 and the secondary body 132 are separated by a free space 133 of any material of electrode, electrolyte and / or current-collecting substrate, connecting the edges 103 and 104, ie extending between the longitudinal edges 103 and 104.
• the 2 free spaces 113 and 133 are mutually symmetrical, with respect to the median axis Y100.
• each free space 113 corresponds to the width of the channel 18, belonging to the slot described in the previous figures.
• the width L112 of each body secondary 112 corresponds to the distance D20, as described with reference to FIG. 6 or to FIG. 8.
• FIG. 13 illustrates an additional variant of the invention.
• the mechanical elements similar to those of FIGS. 1 to 1 1 illustrating the first embodiment are assigned thereto the same reference numbers increased by the number 1000.
• This second embodiment differs from the first variant essentially in that the H-shaped slots 1014 are distributed along lines L1 to L y , arranged one below the other, as well as in rows Ri to R x provided one next to the other. In this way at least one of the main vertical recesses 1016 of the slot positioned in row R n is merged with at least one of the main vertical recesses 1016 of the adjacent slot positioned in row R n -i and / or R n + i . In this case, the two adjacent rows are not separated by strips of material. As shown in FIG. 13, two adjacent lines are separated by bridges of material 1020, the height of which H1020 is noted, which is between 0.05 mm and 5 mm. These material bridges give the anode and cathode sheets sufficient mechanical rigidity so that they can be easily handled.
• the H-shaped slots 1014 can preferably be the same as in the first variant.
• the slot 1014 is preferably formed by two main vertical and parallel recesses 1016, which are connected in their upper part by a horizontal channel 1018, preferably perpendicular to the two main vertical recesses 1016.
• Each cathode is provided with different lines and rows of slots 1014.
• Each anode is also provided with different lines and rows of slots 1034, provided in the same number as the slots 1014.
• each slot 1034 is substantially similar to that of each slot 1014, namely that this slot 1034 comprises two vertical main recesses 1036, connected by a channel 1038.
• the dimensions of the vertical main recesses 1036 are identical to those of the main vertical recesses 1016 and, similarly, the dimensions of the channels 1038 are similar to those of the channels 1018.
• the vertical main recesses 1036 are superimposed with the vertical main recesses 1016.
• the channels 1018 and 1038 are mutually symmetrical when viewed from above, with respect to the median axis of the H, which is denoted XH '.
• Each cut is made between a respective channel and the end opposite the H. It is assumed that the thickness of said cut is neglected.
• the cuts are made both through the anodes and the cathodes, namely at a distance D1020 from the channels of the H-shaped slots so as to have for each cathode 1110, respectively each anode 1130 of the battery 1100, a main body. 1111, respectively 1131, separated from a secondary body 1112, respectively 1132, by a free space of any electrode material, electrolyte and / or current-collecting substrate 1113, respectively 1133, as illustrated in FIG. 15
• This is a particularly advantageous characteristic of the invention, since it makes it possible to improve the quality of the cut with regard to the prior art and to avoid the presence of short circuit at the side edges.
• Each final battery 1100 is delimited, at the top and bottom, by the two cutouts and, on the right and left, by the interior faces of the main vertical recesses of the H.
• the 1100 batteries were hatched once cut by the cutting lines D n and D ' n , areas 1040 of the sheets of the stack, which do not form the batteries, have been illustrated with points, while the volume of the slots is left in white.
• each cathode 1110 comprises a main body 1111, a secondary body 1112 situated on a first lateral edge 1101, as well as a space 1113 free of any material of electrode, electrolyte and / or collector substrate current.
• the latter whose width corresponds to that of the channel 1018 of the slot 1014 described above, extends between the longitudinal edges.
• each anode 1130 comprises a main body 1131, as well as a secondary body 1132 situated on the lateral edge 1102, opposite to that 1101.
• the main body 1131 and the secondary body 1132 are separated by a free space 1133 from any material of electrode, electrolyte and / or current collector substrate, connecting the longitudinal edges, ie extending between the longitudinal edges 1103 and 1104.
• the 2 free spaces 1113 and 1133 are mutually symmetrical, with respect to the median axis Y100.
• each free space 1113 corresponds to the width of the channel 1018, belonging to the slot described in the preceding figures. Furthermore, the width L1112 of each secondary body 1112 corresponds to the distance D1020, as described above.
• the battery 1100 obtained according to the second variant of the invention is in all respects identical to that obtained according to the first variant of the invention even though the arrangement of the slots 1014 is different.
• the H-shaped slots 14/1014 can be distributed along lines L1 to L y , arranged one below the other, as well as according to rows Ri to R provided next to each other.
• the H-shaped slots 14/1014 are arranged according to the first and second variant of the invention, on the anode sheets and / or cathode, so as to maintain sufficient mechanical rigidity so that these sheets can be handled easily and so that the stack can advantageously define a maximum of unitary batteries.
• the battery 1100 obtained according to the third variant of the invention is identical in all respects to that obtained according to the first and / or second variants according to the invention even though the arrangement of the slots 14/1014 on the anode sheets and / or cathode is different.
• the “free face of the secondary body” corresponds to the face belonging to the secondary body which is opposite to the main body.
• the “free face of the main body” corresponds to the face belonging to the main body which is opposite to the secondary body.
• the use of a rigid structure according to the invention makes it possible to facilitate encapsulation and to reduce the thicknesses of encapsulation with regard to the prior art.
• Encapsulation systems of the multilayer type with thinner and more rigid layers than those of the prior art can be envisaged.
• the heat treatment of the latter allowing the battery to be assembled is carried out at a temperature between 50 ° C and 500 ° C, preferably at a temperature below 350 ° C, and / or mechanical compression of the stack of anode and cathode sheets to be assembled is carried out at a pressure between 10 and 100 MPa, preferably between 20 and 50 MPa.
• the stack of anode sheets and sheets of cathode according to the invention can be covered with a sequence, preferably with z sequences, of an encapsulation system comprising:
• a first covering layer preferably chosen from parylene, type F parylene, polyimide, epoxy resins, silicone, polyamide and / or a mixture thereof, deposited on the stack of sheets 'anode and cathode,
• a second covering layer composed of an electrically insulating material, deposited by depositing atomic layers on said first covering layer.
• This sequence can be repeated z times with z> 1.
• This multilayer sequence has a barrier effect. The more the sequence of the encapsulation system is repeated, the greater this barrier effect. It will be all the more important as the number of thin layers deposited will be important.
• the first covering layer is made of polymer, for example silicone (deposited for example by impregnation or by chemical vapor deposition assisted by plasma from hexamethyldisiloxane (HMDSO)), or epoxy resin, or polyimide, polyamide, or poly-para-xylylene (better known by the term parylene).
• This first covering layer protects the sensitive elements of the battery from its environment.
• the thickness of said first covering layer is preferably between 0.5 pm and 3 pm.
• the first covering layer can be made of type C parylene, type D parylene, type N parylene (CAS 1633-22-3), type F parylene or a mixture of type C, D parylene , N and / or F.
• Parylene also called polyparaxylylene or poly (p-xylylene)
• Parylene is a dielectric, transparent, semi-crystalline material which has high thermodynamic stability, excellent resistance to solvents and very low permeability. Parylene also has barrier properties that protect the battery from its external environment. Battery protection is increased when this first covering layer is made from type F parylene.
• This first covering layer is advantageously obtained from the condensation of gaseous monomers deposited by chemical vapor deposition (CVD) on the surfaces, which allows a conformai, thin and uniform covering of all the accessible surfaces of the stack.
• This first covering layer is advantageously rigid; it cannot be considered a flexible surface.
• the second covering layer is composed of an electrically insulating material, preferably inorganic.
• This second covering layer advantageously has a very low WVTR coefficient, preferably less than 10 -5 g / m 2 .d. It is preferably deposited by depositing atomic layers (ALD), so as to obtain a conformal covering of all the accessible surfaces of the stack previously covered with the first covering layer.
• the layers deposited by ALD are very fragile mechanically and require a rigid support surface to ensure their protective role.
• the deposition of a fragile layer on a flexible surface would lead to the formation of cracks, causing a loss of integrity of this protective layer.
• the growth of the layer deposited by ALD is influenced by the nature of the substrate.
• a layer deposited by ALD on a substrate having zones of different chemical natures will have an inhomogeneous growth, which can cause a loss of integrity of this protective layer.
• the ALD deposition techniques are particularly well suited for covering surfaces with high roughness in a completely waterproof and conforming manner. They make it possible to produce conformal layers, free from defects, such as holes (so-called “pinhole free” layers, i.e. free from holes) and represent very good barriers. Their WVTR coefficient is extremely low. The WVTR (water vapor transmission rate) coefficient is used to assess the water vapor permeance of the encapsulation system. The lower the WVTR coefficient, the more waterproof the encapsulation system.
• the second covering layer can advantageously be deposited by chemical vapor deposition assisted by plasma (or PECVD, for Plasma-Enhanced Chemical Vapor Deposition) or by chemical vapor deposition of HDPCVD type (High Density Plasma Chemical Vapor Deposition in English) or ICP CVD (Inductively Coupled Plasma Chemical Vapor in English) type.
• PECVD Plasma-Enhanced Chemical Vapor Deposition
• HDPCVD type High Density Plasma Chemical Vapor Deposition in English
• ICP CVD Inductively Coupled Plasma Chemical Vapor in English
• This second covering layer preferably has a thickness between 10 nm and 10 ⁇ m, preferably a thickness between 10 nm and 50 nm.
• the thickness of this second layer is advantageously chosen as a function of the desired level of gas tightness, i.e. of the desired WVTR coefficient and depends on the deposition technique used, in particular among ALD, PECVD, HDPCVD and ICPCVD.
• the second covering layer may be made of ceramic material, glassy material or glass-ceramic material, for example in the form of oxide, of Al 2 0 3 type , of Ta2C> 5, silica, nitride, especially silicon nitride, phosphates, oxynitride, or siloxane.
• This second covering layer deposited by ALD, PECVD, HDPCVD or ICP CVD on the first covering layer makes it possible, on the one hand, to ensure the tightness of the structure, ie to prevent the migration of water to the inside the object and on the other hand to protect the first covering layer, preferably of type F parylene, from the atmosphere, in particular from air and humidity, from thermal exposures in order to avoid its degradation.
• This second covering layer improves the life of the encapsulated battery.
• the encapsulation system making it possible to ensure the protection of the battery cell, or of the stack of anode sheets and cathode sheets according to the invention, with respect to the the atmosphere may consist of a sequence, preferably of z 'sequences, comprising a first alternative covering layer having a very low WVTR coefficient, preferably less than 10 5 g / m 2 .d.
• This sequence can be repeated z 'times with z> 1. It has a barrier effect, which is all the more important the higher the value of z'.
• the encapsulation of the stack of anode and cathode sheets in this sequence of the encapsulation system makes it possible to reduce the WVTR coefficient of the encapsulation as much as possible, ie to increase the tightness of stacking.
• the thickness of said first alternative covering layer is preferably between 0.5 ⁇ m and 50 ⁇ m.
• This alternative covering layer can be composed of a ceramic material and / or a glass with a low melting point, preferably a glass with a melting point of less than 600 ° C., deposited on the outer periphery of stacking of anodic and cathodic sheets.
• the ceramic and / or glass material used in this layer is advantageously chosen from:
• a glass with a low melting point typically ⁇ 600 ° C
• a low melting point typically ⁇ 600 ° C
• S1O 2 -B 2 O 3 B1 2 O3- B 2 O 3 , Z h O-B ⁇ 2 q 3 -B 2 q 3 , Te0 2 -V 2 0s, PbO-Si0 2 ,
• These glasses can be deposited by molding or by dip-coating.
• the ceramic materials are advantageously deposited by PECVD or preferably by HDPCVD or by ICP CVD at low temperature; these methods make it possible to deposit a layer having good sealing properties.
• the alternative encapsulation system can comprise z ’alternative covering layers of different nature in order to reduce the WVTR coefficient of the encapsulation, i.e. to increase the tightness of the stack.
• the encapsulation system can comprise a first layer composed of a ceramic material, a second layer composed of a glass with low melting point disposed on the first layer, and vice versa.
• the encapsulation in a glass film can be obtained by depositing an ink comprising oxides, phosphates, borates and or precursors of a glass with a low melting point, followed by sintering.
• This provides a rigid and sealed encapsulation, which in particular prevents the passage of water vapor at the interface between the encapsulation system and the terminations.
• the measurement of the water vapor permeance can be done using a method which is the subject of US 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.
• the stack of anode and cathode sheets thus encapsulated in this sequence of the encapsulation system can then be coated with a last covering layer so to mechanically protect the stack thus encapsulated and possibly give it an aesthetic appearance.
• This last covering layer protects and improves the life of the battery.
• this last covering layer is also chosen to withstand a high temperature, and has sufficient mechanical strength to protect the battery during its subsequent use.
• the thickness of this last covering layer is between 1 ⁇ m and 50 ⁇ m. Ideally, the thickness of this last covering layer is approximately 10-15 ⁇ m, such a range of thickness makes it possible to protect the battery against mechanical damage.
• This last covering layer is preferably based on epoxy resin, polyethylene naphthalate (PEN), polyimide, polyamide, polyurethane, silicone, sol-gel silica or organic silica.
• this last covering layer is deposited by dipping.
• the stack of anode and cathode sheets thus coated is then cut by any appropriate means along the cut lines D ′ n and D n so as to expose the anode and cathode connections and to obtain unitary batteries.
• the impregnation of the battery with a liquid electrolyte is advantageously carried out, after obtaining the unit batteries whose anodic and cathodic connections are bare, by a phase carrying lithium ions such as liquid electrolytes or an ionic liquid containing lithium salts; this phase carrying lithium ions enters the battery by capillary action.
• Terminations are added at the level where the cathode, respectively anode, connections are apparent (not coated with insulating electrolyte). These contact areas are preferably arranged on opposite sides of the battery stack to collect current (lateral current collectors) or on adjacent sides.
• the connections are metallized using techniques known to those skilled in the art, preferably by immersion in a conductive epoxy resin and / or a bath of molten tin.
• the terminations consist, near the cathode and anode connections, of a first stack of layers successively comprising a first layer of a material loaded with graphite, preferably of epoxy resin loaded with graphite, and a second layer comprising metallic copper obtained from an ink loaded with copper nanoparticles deposited on the first layer.
• This first stack of terminations is then sintered by an infrared flash lamp so as to obtain a covering of the cathodic and anodic connections by a layer of metallic copper.
• the terminations may additionally comprise a second stack of layers disposed on the first stack of terminations successively comprising a first layer of a deposited tin-zinc alloy, preferably by dipping in a molten tin-zinc bath, in order to ensure leaktightness of the battery at a lower cost and a second layer based on pure tin deposited by electrodeposition or a second layer comprising a silver-based alloy, of palladium and copper deposited on this first layer of the second stack.
• the terminations allow the alternating positive and negative electrical connections to be taken up on each of the ends. These endings allow to realize electrical connections in parallel between the different battery cells. For this, only the cathode connections exit on one end, and the anode connections are available on another end.
• the battery according to the invention can be a lithium ion microbattery, a lithium ion minibattery, 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 “microbattery”), so as to have a power greater than approximately 1 mA h up to approximately 1 A h ( commonly called “mini-battery”), or so as to have a capacity greater than about 1 A h
• microbatteries are designed to be compatible with microelectronics manufacturing processes.
• the batteries of each of these three power ranges can be produced: - either with “all solid” type layers, ie devoid of impregnated liquid or pasty phases (said liquid or pasty phases possibly being a conductor 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 medium conducting lithium ions, which spontaneously enters the layer and which no longer comes out of this layer, so that this layer can be considered as quasi-solid,
• impregnated porous layers i.e. layers having a network of open pores which can be impregnated with a liquid or pasty phase, and which gives these layers wet properties.

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