Lithium-ion battery and method of manufacturing the same
Patent Information
- Application Number
- KR1020227037934
- Authority / Receiving Office
- KR · KR
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2020-03-30
- Filing Date
- 2021-03-23
- Publication Date
- 2026-09-09
- Estimated Expiration
- 2041-03-23
Smart Images
Figure 112022114518288-PCT00010_ABST
Abstract
Description
Technology Field
[0001] The present invention relates to the field of batteries, and more specifically to lithium-ion batteries. The present invention relates to a lithium-ion battery having a novel architecture that provides a longer lifespan. The present invention also relates to a novel method for manufacturing such a battery. Background Technology
[0002] Rechargeable all-solid-state lithium-ion batteries are known. International patent document WO 2016 / 001584 (I-TEN) describes a lithium-ion battery manufactured from an anode foil comprising a conductive substrate continuously covered with an anode layer and an electrolyte layer, and a cathode foil comprising a conductive substrate continuously covered with a cathode layer and an electrolyte layer, wherein the foils are cut into a U-shaped pattern before or after deposition. These foils are then alternately stacked to form a stack of multiple unit cells. The anode and cathode foil cutting patterns are arranged in a "head-to-tail" configuration so that the stacking of the cathode and anode is offset laterally. After the stacking step, a thick layer encapsulation system approximately 10 microns thick is deposited in the stack and in available cavities present within the stack. This first ensures structural rigidity at the cut surface and second protects the battery cells from the atmosphere. When a stack is created and encapsulated, it is cut along the cut planes to obtain individual batteries, and the cathode and anode connection regions of the battery are exposed on each cut plane. When such cutting is performed, the encapsulation system may be torn, potentially damaging the battery's impermeable seal. It is known that terminations (i.e., electrical contacts) are also added where these cathode and anode connection regions are exposed.
[0003] These known solutions have several drawbacks. More specifically, depending on the positioning of the electrodes, particularly the proximity of the electrode edges for multilayer batteries, and the cleanliness of the cut sections, leakage current can appear at the ends, generally in the form of creeping short circuits. These creeping short circuits reduce battery performance despite the use of encapsulation systems around the battery and near the cathode and anode connection regions. Additionally, unsatisfactory deposition of the encapsulation system on the battery is sometimes observed, particularly in the spaces on the battery edges created by the lateral offset of the electrodes on the battery edges.
[0004] U.S. patent document US 2018 / 212210 filed by Suzuki also discloses a battery comprising a plurality of unit cells for the first time. The resulting stack is placed in a metal casing into which a resin is inserted. This mechanically secures the cells so that they do not move during operation. This resin also prevents the risk of a short circuit that could occur when the cells come into contact with the metal casing, particularly during potential shock or vibration.
[0005] Finally, Japanese patent document JP 2007 / 005279 filed by Matsushita is cited. This document discloses an all-solid-state battery obtained by sintering. Accordingly, this battery does not include an electrolyte material or a separator layer impregnated with such an electrolyte. The problem to be solved
[0006] The present invention aims to overcome at least some of the aforementioned disadvantages of the prior art, and in particular aims to provide rechargeable lithium-ion batteries having high energy density and high power density.
[0007] In particular, the aim is to increase the production volume of rechargeable lithium-ion batteries with high energy density and high power density, and to produce more efficient encapsulations at a low cost.
[0008] In particular, the purpose is to propose a method that reduces the risk of creeping or sudden short circuits and enables the manufacture of a battery with a low self-discharge rate.
[0009] In particular, the purpose is to propose a method that enables the manufacturing of batteries with a very long lifespan in a simple, stable, and fast manner.
[0010] In addition, the invention aims to propose a simple, rapid, and cost-effective battery manufacturing method. means of solving the problem
[0011] The present invention first relates to a battery comprising at least one unit cell, wherein each unit cell comprises, in succession, an anode current collector, an anode layer, at least one layer of an electrolyte material and / or at least one layer of a separator impregnated with an electrolyte, a cathode layer, and a cathode current collector.
[0012] When the above battery includes a plurality of unit cells, the unit cells are positioned below each other, that is, overlapped along the frontal direction with respect to the main plane of the battery, preferably:
[0013] The above anode current collection substrate is the anode current collection substrate of two adjacent unit cells, and
[0014] The above cathode current collector is a cathode current collector of two adjacent unit cells, and
[0015] The above at least one unit cell or the unit cells define a stack, and
[0016] The stack and the battery have six sides, i.e.,
[0017] ㆍ Opposing each other, particularly parallel to each other, one or more anode current collector substrates, one or more anode layers, one or more layers of an electrolyte material or one or more layers of a separator impregnated with an electrolyte, one or more cathode layers, and two so-called end planes generally parallel to one or more cathode current collector substrates,
[0018] ㆍ Two so-called sides facing each other, particularly parallel to each other, and
[0019] ㆍ Having two so-called longitudinal planes that face each other, particularly parallel to each other,
[0020] The first longitudinal surface of the battery includes at least one anode connection area, and the second longitudinal surface of the battery includes at least one cathode connection area, and the anode and cathode connection areas face each other laterally.
[0021] - In the first longitudinal direction of the above battery, each anode current collector substrate protrudes from each anode layer, each layer of electrolyte material or layer of separator impregnated with electrolyte, each cathode layer, and each cathode current collector substrate layer, and
[0022] - In the second longitudinal direction of the battery opposite to the first longitudinal direction, each cathode current collection substrate is characterized by protruding from each anode layer, each layer of electrolyte material or layer of separator impregnated with electrolyte, each cathode layer, and each anode current collection substrate layer.
[0023] In one specific embodiment:
[0024] - Each anode current collector substrate protrudes from a first end plane, which is defined by a first longitudinal end of each anode layer, each layer of electrolyte material or separator layer, each cathode layer and each cathode current collector substrate layer, and / or
[0025] - Each cathode current collector substrate protrudes from a second end plane, and this second plane is defined by each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and a second longitudinal end of each anode current collector substrate layer.
[0026] According to a particularly advantageous embodiment of the present invention, a battery according to the present invention comprises an encapsulation system covering at least a portion of the outer periphery of a stack, and said encapsulation system 10 -5 g / m 2 The encapsulation system comprises at least one impermeable cover layer having a water vapor permeability (WVTR) of less than .d, and the encapsulation system is in direct contact with at least the electrolyte material layer and / or the separator layer impregnated with the electrolyte on each longitudinal side. Preferably, the encapsulation system is also in direct contact with an anode layer, a cathode layer, and a non-protruding current collector substrate on each longitudinal side.
[0027] Advantageously, the encapsulation system is electrically insulated, and the conductivity of the encapsulation system is advantageously 10 e-11 Sm -1 Less than, especially 10 e-12 Sm -1 It is less than.
[0028] Advantageously, the encapsulation system covers at least a portion of the outer periphery of the stack, and the encapsulation system covers at least a portion of the end face, side face, and longitudinal face of the stack,
[0029] - Only the anode edge of each anode current collector protruding in the first longitudinal direction of the battery from each anode layer, each layer of electrolyte material or separator layer, each cathode layer and each anode current collector substrate layer is positioned at the same height as the first longitudinal plane, and
[0030] - Only the cathode edge of each cathode current collector protruding in the second longitudinal direction of the battery from each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each anode current collector substrate layer is positioned at the same height as the second longitudinal plane, and the second longitudinal plane is preferably opposite to and parallel to the first longitudinal plane, and
[0031] Each anode edge defines an anode connection region and each cathode edge defines a cathode connection region.
[0032] According to another aspect of the present invention, the encapsulation system is:
[0033] - Optionally, preferably selected from parylene, parylene F, polyimide, epoxy resin, silicone, polyamide, sol-gel silica, organic silica, and / or mixtures thereof, a first cover layer deposited on at least a portion of the outer periphery of the stack,
[0034] - Optionally, a second cover layer composed of an electrical insulating material deposited by atomic layer deposition on at least a portion of the outer periphery of the stack or on the first cover layer,
[0035] - Preferably 10 -5 g / m 2 At least a third impermeable cover layer having a water vapor transmittance (WVTR) of less than .d, wherein the third cover layer is made of a ceramic material and / or low-melting-point glass, preferably glass with a melting point of less than 600°C, and comprises at least a third impermeable cover layer deposited on at least a portion of the outer periphery of the stack or on the first cover layer.
[0036] When the above second cover layer exists,
[0037] - The sequence of the second cover layer and the third cover layer may be repeated z times, where z≥1, and is deposited on at least the outer circumference of the third cover layer,
[0038] - The last layer of the encapsulation system is an impermeable cover layer, preferably 10 -5 g / m 2 It has a water vapor permeability (WVTR) of less than .d and is made of ceramic material and / or low-melting point glass.
[0039] According to another aspect of the present invention, at least an anode connection area, preferably a first longitudinal surface comprising at least an anode connection area, is covered by an anode contact member, and at least a cathode connection area, preferably a second longitudinal surface, comprises at least a cathode connection area and is covered by a cathode contact member, and
[0040] The above anode and cathode contact members can create electrical contact between the stack and the external conductive element.
[0041] According to another aspect of the present invention, each of the anode and cathode contact members is:
[0042] - A first electrical connection layer disposed on at least an anode connection region and at least a cathode connection region, preferably on a first longitudinal plane including at least an anode connection region and a second longitudinal plane including at least a cathode connection region,
[0043] The first layer comprises a first electrical connection layer comprising electrically conductive particles, preferably a polymer resin and / or a material obtained by a sol-gel method, electrically conductive particles and, more preferably, a material filled with a graphite-filled polymer resin, and
[0044] - Includes a second electrical connection layer comprising a metal foil disposed on a first layer of a material filled with electrically conductive particles.
[0045] According to another aspect of the present invention, the smallest distance between a first end plane defined by a first longitudinal end of each anode layer, each layer of electrolyte material and / or separator layer, each cathode layer, and each cathode current collection substrate layer, and a first longitudinal plane including at least one anode connection zone is configured to be 0.01 mm to 0.5 mm, and / or
[0046] The smallest distance between a second end plane defined by each anode layer, each layer of electrolyte material and / or separator layer, and a second longitudinal plane including at least one cathode connection zone, and a second longitudinal plane defined by a second longitudinal end of each anode layer and each anode current collection substrate layer is configured to be between 0.01 mm and 0.5 mm.
[0047] The present invention also relates to a method for manufacturing at least one battery, and
[0048] Each battery includes at least one unit cell, and
[0049] Each unit cell comprises, in succession, an anode current collector, an anode layer, at least one layer of an electrolyte material and / or at least one layer of a separator impregnated with an electrolyte, a cathode layer, and a cathode current collector.
[0050] When the above battery includes a plurality of unit cells, the unit cells are positioned below each other, that is, overlapped according to the frontal direction with respect to the main plane of the battery, preferably:
[0051] The above anode current collection substrate is the anode current collection substrate of two adjacent unit cells, and
[0052] The cathode current collector is the cathode current collector of two adjacent unit cells, and
[0053] The above at least one unit cell or the unit cells define a stack, and
[0054] The stack and the battery have six sides, i.e.,
[0055] - Two so-called end planes facing each other, particularly parallel to each other, generally comprising one or more anode current collectors, one or more anode layers, one or more layers of an electrolyte material or one or more layers of a separator impregnated with an electrolyte, one or more cathode layers, and one or more cathode current collectors, parallel to the cathode current collectors.
[0056] - Two so-called sides facing each other, especially parallel to each other, and
[0057] - Having two so-called longitudinal planes that face each other, and in particular parallel to each other,
[0058] A first longitudinal surface of the battery includes at least one anode connection region and a second longitudinal surface of the battery includes at least one cathode connection region, and the anode and cathode connection regions are laterally opposite each other,
[0059] - In the first longitudinal direction of the battery, each anode current collector substrate protrudes from each anode layer, from each layer of the electrolyte-impregnated separator or electrolyte material, from each cathode layer, and from each cathode current collector substrate layer, and
[0060] - In the second longitudinal direction of the battery opposite to the first longitudinal direction above, each anode current collection substrate protrudes from each anode layer, from each layer of electrolyte material or from a layer of separator impregnated with electrolyte, from each cathode layer and from each anode current collection substrate layer, and
[0061] The above manufacturing method is:
[0062] A first step of supplying at least one anode current collector substrate foil (hereinafter referred to as an anode foil) having a groove, an uncoated area, and an area coated with an anode layer and optionally coated with an electrolyte material layer or a separator layer,
[0063] A second step of supplying at least one cathode current collector substrate foil (hereinafter referred to as cathode foil) having a groove, an uncoated area, and a cathode layer, optionally coated with an electrolyte material layer or a separator layer,
[0064] As a third step of generating an alternating stack of at least one cathode foil having a groove, an uncoated area, and a coated area and at least one anode foil having a groove, an uncoated area, and a coated area to obtain at least one unit cell comprising an anode current collector substrate, an anode layer, at least one layer of an electrolyte material or separator, a cathode layer, and a cathode current collector substrate,
[0065] In the first longitudinal direction of the battery, each anode current collector substrate protrudes from each anode layer, each layer of electrolyte material and / or separator layer, each cathode layer, and each cathode current collector substrate layer, and
[0066] A third step in which, in a second longitudinal direction of the battery opposite to the first longitudinal direction above, each cathode current collector substrate protrudes from each anode layer, each layer of electrolyte material and / or separator layer, each cathode layer, and each anode-current collector substrate layer,
[0067] Step 4, heat-treating and / or mechanically compressing the stack of alternating foils obtained in Step 3 to form an integrated stack,
[0068] Optionally, a fifth step of making a first cutting pair that allows a given battery line to be separated from at least one other battery line formed from the integrated stack,
[0069] Step 6, optionally impregnating the integrated stack obtained in Step 4, or when this Step 5 is performed, impregnating the battery line obtained in Step 5 with a phase having lithium ions, such as a liquid electrolyte or an ionic liquid containing a lithium salt, so that the separator layer is impregnated by the electrolyte.
[0070] Optionally create a second cutting pair
[0071] - The anode edge of each anode current collector protruding in the first longitudinal direction of the battery from each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each cathode current collector substrate layer is exposed so that each anode edge defines at least one anode connection region, and
[0072] - The cathode edge of each cathode current collector protruding in the second longitudinal direction of the battery from each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each cathode current collector substrate layer is exposed so that each cathode edge defines at least one cathode connection region, and
[0073] When the above 5th step is performed, the method includes a 7th step in which the battery given by the 2nd cutting pair can be separated from at least one other battery formed from the battery line.
[0074] In one specific embodiment of this method, after step 6 (if performed), or if step 6 is not performed, after step 5 (if performed), or if steps 6 and 5 are not performed, after step 4 and before step 7, step 8 of encapsulating the integrated stack or battery line is performed, wherein preferably at least a portion of the outer periphery of the stack or battery line, preferably at least a portion of the longitudinal face, side face, and longitudinal face of the stack or battery line, is covered with an encapsulation system,
[0075] Only the anode edge of each anode current collector protruding in the first longitudinal direction of the battery from each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each cathode current collector substrate layer is positioned at the same height as the first longitudinal plane, and
[0076] ο Each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each cathode current collector substrate protruding in the second longitudinal direction of the battery from each cathode current collector substrate layer are positioned at the same height as the second longitudinal plane, so that the second longitudinal plane is preferably opposite and parallel to the first longitudinal plane, and
[0077] Each anode edge defines an anode connection region and each cathode edge defines a cathode connection region;
[0078] The above encapsulation system is preferably,
[0079] - Optionally, preferably selected from parylene, parylene F, polyimide, epoxy resin, silicone, polyamide, sol-gel silica, organic silica, and / or mixtures thereof, at least one first cover layer deposited on the outer periphery of the stack or at least a portion of the battery line,
[0080] - Optionally, a second cover layer composed of an electrical insulating material deposited by atomic layer deposition,
[0081] - At least part of the outer perimeter of the stack or battery line,
[0082] - or on the first cover layer, and
[0083] - Preferably 10 -5 g / m 2At least one third impermeable cover layer having a water vapor permeability (WVTR) of less than .d, wherein the third cover layer is made of a ceramic material and / or low-melting-point glass, preferably glass with a melting point of less than 600°C, and comprises at least one third impermeable cover layer deposited on at least a portion of the outer periphery of a stack or battery line or on a first cover layer.
[0084] A sequence of at least one second cover layer and at least one third cover layer may be repeated z times, where z ≥ 1, and is deposited on the outer periphery of at least the third cover layer, and the last layer of the encapsulation system is preferably 10 -5 g / m 2 It is an impermeable cover layer made of ceramic material and / or low-melting point glass having a water vapor permeability (WVTR) of less than .d.
[0085] In another specific embodiment of the method according to the present invention that can be combined with the above, after step 7, at least a first longitudinal surface including at least an anode connection area, preferably at least an anode connection area, is covered by an anode contact member capable of creating electrical contact between the stack and an external conductive element, and
[0086] At least a cathode connection area, preferably at least a second longitudinal surface including at least a cathode connection area, is covered by a cathode contact member capable of creating electrical contact between the stack and an external conductive element, and
[0087] The manufacture of the above anode and cathode contact members is:
[0088] - A step of depositing a first electrical connection layer made of a material filled with electrically conductive particles on at least an anode connection region and at least a cathode connection region, preferably on at least a first longitudinal plane including at least an anode connection region and at least a second longitudinal plane including at least a cathode connection region, wherein the first layer is preferably made of a material obtained by a sol-gel method filled with a polymer resin and / or electrically conductive particles,
[0089] - Optionally, if the first layer is prepared from a material obtained by a sol-gel method filled with a polymer resin and / or electrically conductive particles, a drying step followed by a drying step followed by a step of polymerizing said polymer resin and / or said material obtained by the sol-gel method, and
[0090] - A step of depositing a second electrical connection layer comprising a metal foil disposed on the first electrical connection layer on the first layer, and
[0091] - Optionally, the step of depositing a third electrical connection layer containing conductive ink on the second electrical connection layer. Brief explanation of the drawing
[0092] The attached drawings, given as non-limiting examples, illustrate other aspects and embodiments of the present invention. FIG. 1 is a perspective view of an anode and a cathode foil intended to form a stack according to a battery manufacturing method according to the present invention, and the anode and cathode foils have a unit body comprising an uncoated area, a coated area and a groove. FIG. 2 is a front view showing one of the foils, specifically the anode foil of FIG. 1. FIG. 3 is a front view illustrating, at a larger scale, a unit object composed of an uncoated area, a coated area, and a groove, manufactured in an anode foil according to the present invention or an alternative embodiment of the present invention, referred to hereinafter using the term "exclusion area." FIG. 4 is a large-scale perspective view showing the non-coated or excluded area, coated area, and groove of these unit objects provided on adjacent foils. FIG. 5 is a plan view showing a cutting step performed on different unit objects provided in a stack of the preceding drawings. Figure 6 is a plan view showing a section made from a unit object on a larger scale. FIG. 7 is a cross-sectional view along the cutting line VII-VII shown in FIG. 6, illustrating a stack of anode and cathode unit entities according to the present invention or an alternative embodiment of the present invention, each of which consists of an uncoated area, a coated area, and a groove. FIG. 8 is a cross-sectional view along the cutting line VII-VII shown in FIG. 6, illustrating a stack of unit entities encapsulated in an encapsulation system. FIG. 9 is a cross-sectional view along the cutting line VII-VII illustrating a battery according to the present invention, including an encapsulation system that can be obtained in particular according to the method illustrated in the prior art. FIG. 10 is a perspective view illustrating a battery according to the present invention, including an encapsulation system that can be obtained in particular according to the method illustrated in the prior art. FIG. 11 is a cross-sectional view along cutting line VII-VII showing a battery according to the present invention, comprising an encapsulation system and a contact member, which can be obtained in particular according to the method illustrated in the prior art. FIG. 12 is a perspective view showing a battery according to the prior art. FIG. 13 is a front view showing one of the foils according to an alternative embodiment of the present invention, in particular an anode foil in which the anode exclusion region is formed in the form of a single exclusion strip. FIG. 14 is a plan view illustrating a cutting step performed on different unit objects provided in a stack according to an alternative embodiment of the present invention. FIG. 15 is a plan view illustrating a cutting step performed on different unit objects provided in a stack according to an alternative embodiment of the present invention and illustrating a battery obtained according to this alternative embodiment. FIG. 16 is a plan view illustrating a battery line according to the present invention. FIG. 17 is a perspective view illustrating a battery line according to the present invention, including an encapsulation system that can be obtained in particular according to the method illustrated in the prior art. FIGS. 18 to 20 are front views illustrating successive steps for manufacturing a battery according to another embodiment of the present invention, wherein the battery comprises a single cell and each current collector forms a tab. FIG. 21 is a front view similar to FIG. 8 and illustrates a battery according to an alternative embodiment of the battery of FIG. 8. FIGS. 22 to 24 are front views similar to the front views of FIGS. 18 to 21, illustrating a continuous step of manufacturing a battery according to another embodiment of the present invention using a metal grid-type electrical connection support. FIG. 25 is a front view similar to the front view of FIG. 24 and illustrates an alternative embodiment of FIG. 24. The following reference numerals are used in the drawings and the description below: 1000, 1000' Battery according to the present invention 1002 Anode Connection Zone 1002' anode edge of each anode current collection board 1006 Cathode connection zone 1006' cathode edge of each cathode current collector substrate 100, 100', 100" unit cell 10 anode current collector boards 20 anode layers 30 Layer of electrolyte material / Electrolyte layer 31 Layer of a membrane impregnated with an electrolyte or continuously impregnated / membrane layer 40 cathode current collector board 50 cathode layers 60 unit objects 60' anode unit object 60" cathode unit object 70 I-shaped groove / cathode groove of cathode foil H 70 The total height of the I-shaped cathode groove (70) L 70 The full width of the I-shaped cathode groove (70) 71 Coated area of the cathode foil 72 Cathode foil exclusion area / non-coated area / cathode exclusion area L 72 The full width of the exclusion area / uncoated area (72) of the cathode foil H 72 The total height of the exclusion area / uncoated area (72) of the cathode foil L 71 The full width of the coated area of the cathode foil 80 I-shaped grooves / anode grooves of anode foil H 80 The total height of the I-shaped anode groove (80) 81 The total width of the I-shaped anode groove (80) 82 Anode foil exclusion area / non-coated area / anode exclusion area 82' excluded strip L 81 The full width of the coated area of the anode foil H 81 The total height of the coated area of the anode foil L 82The full width of the exclusion area / uncoated area (82) H 82 Total height of the exclusion area / uncoated area (82) 90 material debris 95 Encapsulation System 97 Contact member 97' anode contact absence 97'a Anode contact member pin covering the ends of surfaces (F1, F2, F3, F5) adjacent to the longitudinal surface (F6) 97" anode contact absence 97"a A cathode contact member pin covering the ends of surfaces (F1, F2, F3, F5) adjacent to the longitudinal surface (F4) Dca The minimum distance between the first longitudinal plane (F6) and the first end plane (DYa) of a battery (1000) including at least one anode connection area (1002). Dcc Minimum distance between the second longitudinal plane (F4) and the second end plane (DY'a) of a battery (1000) including at least one cathode connection area (1006). Dca' Minimum distance between a first longitudinal plane of a battery (1000') including at least one anode connection region and a first end plane defined by a first longitudinal end of each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each cathode current collection substrate layer. The minimum distance between a second longitudinal plane of a battery (1000') comprising at least one cathode connection region Dcc' and a second end plane defined by a first longitudinal end of each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each anode current collection substrate layer. I 1000 Battery width L 1000 Battery length C 1000 The center of the battery Z 1000Parallel to the front direction (ZZ) of the battery and the center (C) of the battery (1000) 1000 An axis penetrating ) R 1000 Z 1000 Rotation of the battery (1000) around the circumference I. Stack of substrate foils covered by an electrode layer (anode or cathode) and an electrolyte foil or a foil of a separator impregnated with or continuously impregnated with an electrolyte / Stack of at least one unit cell Anode foil with 2e unit entities Cathode foil with 5e unit entities The perforated central part of the anode foil with 4 unit entities The surrounding frame of an anode foil with 6 unit objects 7 Perforations present at the four ends of the substrate, anode, cathode, electrolyte, or foils of the separator impregnated or continuously impregnated with the electrolyte 8 Material bridges between 2 lines The height of H8 bridges 9 Material strips between the two columns The width of L9 strips Longitudinal or horizontal direction of the XX stack / battery YY Lateral or transverse direction of the stack / battery Front view of the ZZ stack / battery L, L n , L n-1 , L n+1 Lines / battery lines of unit objects R, R n , R n-1 , R n+1 Columns of unit objects DY n-1 , DY' n-1 , DY n , DY' n , DY n+1 , DY' n+1 Severed sections DX n-1 , DX' n-1 , DX n, DX' n , DX n+1 , DX' n+1 Severed sections DYa A first end plane of a battery defined by a first longitudinal end of each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each cathode current collector substrate layer. DY'a A second end plane of a battery defined by a second longitudinal end of each anode layer, each layer of electrolyte material or separator layer, each cathode layer, and each anode current collector substrate layer. 2000 Battery according to the prior art 200, 200', 200" Unit cell of a battery according to the prior art 2002 Anode connection area of a battery according to the prior art 2006 Cathode connection area of a battery according to the prior art 295 Battery encapsulation system according to the prior art Side center line of YH unit objects End surface of F1, F2 stack (I) / battery (1000) F3, F5 side of stack(I) / battery(1000) Longitudinal surface of F4, F6 stack (I) / battery (1000) FF1, FF2 battery lines (L n end surface of ) FF3, FF5 battery lines (L n The side of ) FF4, FF6 battery line (L n The side of ) Specific details for implementing the invention
[0093] Generally, the following geometric names are associated with this battery:
[0094] ZZ represents the so-called frontal direction, that is, perpendicular to the plane of different stacked layers.
[0095] XX represents the so-called longitudinal direction that is contained in the plane of the stacked layer and is parallel to the largest dimension of this layer when viewed from above, that is, in the frontal direction.
[0096] YY represents the so-called lateral or transverse direction contained in the plane of the stacked layer and parallel to the smallest dimension of this layer when viewed from above.
[0097] In addition, generally, two directions associated with each of these three directions are provided with reference to the plane of the foil illustrated in FIG. 10.
[0098] Therefore, the right and left directions are associated with the XX direction, the forward and backward directions are associated with the YY direction, and the up and down directions are associated with the ZZ direction with reference to the plane of the foil shown in Fig. 10.
[0099] In addition, generally, a first longitudinal direction (XX') extending from right to left and a second longitudinal direction (XX") extending from left to right, opposite to the first longitudinal direction (XX'), are defined with respect to the plane of the foil illustrated in FIG. 10. Again, with reference to the plane of the foil illustrated in FIG. 10, a first lateral direction (YY') extending from front to back, a second lateral direction (YY") opposite to the first lateral direction, a first frontal direction (ZZ') extending from top to bottom, and a second frontal direction (ZZ") opposite to the first frontal direction are defined.
[0100] The method according to the present invention first comprises the step of creating a stack (I) of alternating foils, the foils being referred to as "anode foils" or "cathode foils" below, depending on the circumstances. As will be known in more detail below, each anode foil is intended to form the anode of a plurality of batteries, and each cathode foil is intended to form the cathode of a plurality of batteries. An example of FIG. 1 illustrates two cathode foils having unit entities (5e) and two anode foils having unit entities (2e). In practice, this stack is generally formed with a larger number of foils, ranging from 10 to 1,000. The number of cathode foils having unit entities (5e) is equal to the number of anode foils having unit entities (2e) used and constitutes a stack (I) of alternating foils of opposite polarity.
[0101] In a favorable embodiment, each of these foils has perforations (7) at four ends so that when these perforations (7) overlap, all cathodes and all anodes of these foils are arranged according to the present invention as described in more detail below (see FIG. 1, FIG. 2, and FIG. 3). These perforations (7) at the four ends of the foils can be made by any suitable means, particularly in the anode and cathode foils after manufacturing, or in the substrate foils (10, 40) before manufacturing the anode and cathode foils. Each anode foil comprises an anode current collecting substrate (10) that is at least partially coated with an active layer (20) of an anode material, which is referred to hereinafter as the anode layer (20). Each cathode foil comprises a cathode current collecting substrate (40) that is at least partially coated with an active layer (50) of a cathode material, which is hereinafter referred to as the cathode layer (50). Each of these active layers may be solid and may have particularly dense or porous properties. Additionally, to prevent electrical contact between two active layers of opposite polarity, an electrolyte layer (30) or a separator layer (31) impregnated with an electrolyte is disposed on at least one of the active layers of these current collecting substrates that is pre-coated with an active layer and is in contact with the opposite active layer. The electrolyte layer (30) or the separator layer (31) may be disposed on the anode layer (20) and / or cathode layer (50); the electrolyte layer (30) or the separator layer (31) forms an integral part of the anode foil and / or cathode foil comprising them.
[0102] Advantageously, two sides of the anode (10) or each cathode (40) current collector substrate may each be at least partially coated with an anode layer (20) or each cathode layer (50), and optionally coated with an electrolyte layer (30) or a separator layer (31) disposed on the anode layer (20) or on the cathode layer (50), respectively. In this case, the anode (10) or each cathode (40) current collector substrate acts as a current collector for two adjacent unit cells (100, 100'). The use of these substrates in batteries increases the production of rechargeable batteries having high energy density and high power density.
[0103] The mechanical structure of one of the anode foils will be described below, and it is understood that the other anode foils have the same structure. Additionally, as can be seen below, the cathode foils have a structure very similar to that of the anode foils.
[0104] As illustrated in FIG. 2, the anode foil (2e) having unit objects (60, 60') has a quadrilateral shape, substantially a square shape. This defines the so-called perforated central area (4) where the unit objects are formed, which will be described below. In relation to the positioning of these unit objects, the so-called lateral or transverse direction (YY) of the foil corresponding to the lateral direction of these unit objects, and the so-called horizontal direction (XX) of the foil perpendicular to the direction (YY) are defined. The central area (4) is defined by a solid, i.e., a peripheral frame (6) without unit objects. The function of this frame is specifically to ensure easy handling of each foil.
[0105] Unit objects (60, 60') are lines (L1 to L) in which one is placed below the other y ) and columns placed next to each other (R1 to R xIt is distributed as follows. By non-limiting example, within the manufacturing range of micro-batteries of surface mount device type (hereinafter referred to as SMD), the anode and cathode foils used may be 100mm × 100mm wafers. Generally, the number of lines of these foils consists of 10 to 500, while the number of columns consists of 10 to 500. As a function of the desired battery capacity, the dimensions may vary, and the number of lines and columns for each anode and cathode foil may be appropriately adjusted. The dimensions of the anode and cathode foils used may be modified according to requirements. As shown in FIG. 2, two adjacent lines may be separated by bridges (8) of material, the height of which is indicated by H8 is 0.05mm to 5mm. Two adjacent rows can be separated by strips (22) of material, the width of which, denoted by L9, is 0.05 mm to 5 mm. These bridges (8) and strips (9) of the material of the anode and cathode foils provide sufficient mechanical rigidity so that the foils can be easily handled.
[0106] The unit entity (60, 60', 60") includes exclusion areas, namely, uncoated areas (72, 82), coated areas (71, 81), and grooves (70, 80) described in more detail below. Preferably, these grooves (70, 80), which are I-shaped, are penetrating, that is, open on the upper and lower opposing surfaces of the foil, respectively. Preferably, these grooves (70, 80) have a quadrature shape, substantially rectangular type. These grooves (70, 80) can be created directly on the current-collecting substrate in a known manner prior to any deposition of an anode or cathode material by chemical etching, electrocasting, laser cutting, microperforation, or stamping. These grooves (70, 80) also:
[0107] - On a current collector substrate at least partially coated with an anode or cathode material layer, or
[0108] - It can be manufactured on a current collector substrate, i.e., an anode or cathode foil, which is at least partially coated with a layer of an anode or cathode material that is coated with an electrolyte layer or a separator layer.
[0109] When the grooves (70, 80) are made in these at least partially coated substrates, the grooves (70, 80) may be manufactured in a manner known in itself, for example, by laser cutting (or laser ablation), femtosecond laser cutting, microperforation, or stamping. The grooves (70) made in all cathode foils overlap each other. The grooves (80) made in all anode foils overlap each other.
[0110] One of the unit objects (60) as illustrated in FIG. 3 will now be described, and all unit objects (60, 60') of the anode foil are identical and all unit objects (60, 60") of the cathode foil are identical.
[0111] FIG. 3 illustrates an anode unit object (60, 60').
[0112] Each unit entity (60, 60', 60") preferably includes an I-shaped through-groove (80, 70), an exclusion area, i.e., an uncoated area (82, 72) and a coated area (81, 71).
[0113] The coated area (81) of the anode unit entity (60') is understood to mean an area of the anode foil covered by the anode layer (20) or covered by the anode layer (20) and the electrolyte layer (30) or the separator layer (31). The excluded area or uncoated area (82) of the anode unit entity (60') is understood to mean an area of the anode foil not covered by the anode layer (20) or covered by the anode layer (20) and the electrolyte layer (30) or the separator layer (31).
[0114] The anode exclusion region (82) is a region where there is no electrolyte material or separator and no anode material. When created on an anode foil, this anode exclusion region (82) is created in such a way that it removes or prevents the deposition of any electrolyte material or separator and any anode material, leaving at least a portion of the anode current collection substrate (10). Consequently, in the first longitudinal direction (XX') of the battery, each anode current collection substrate (10) protrudes from each anode layer (20) and each electrolyte material layer (30) or electrolyte-impregnated separator layer (31). When the current collector substrate is completely covered with an anode layer (20), the substrate itself (20) is optionally covered with an electrolyte layer (30) or a separator layer (31), and an anode exclusion region (82) can be created by laser ablation to locally remove the anode layer (20) coated with the anode layer (20) or the electrolyte layer (30) or the separator layer (31). The anode exclusion region (82) can also be produced by local slot-die coating of the current collector substrate in a manner known in itself. Local slot-die coating of the current collector substrate allows for local deposition of the substrate, particularly the anode layer (20), and optionally subsequently covered with an electrolyte layer (30) or a separator layer (31) in the same manner. Slot-die coating on the substrate symmetric in the direction of movement of the substrate allows the uncoated region (82) to remain directly on the substrate; This reduces the number of steps in the method of manufacturing unit objects on an anode foil.
[0115] On one hand, the exclusion area (82, 72), and on the other hand, the groove (80, 70) of the same unit object (60, 60', 60") are symmetric to each other when viewed from above with respect to the center line of the unit object (60, 60', 60") indicated by YH.
[0116] Each anode exclusion region (82) is created in succession of each cathode home (70), and each cathode exclusion region (72) is created in succession of each anode home (80).
[0117] The anode foil obtained after creating the home (80), coated area (81), and exclusion area (82) is referred to below as an anode foil having a unit entity (2e).
[0118] The following reference numerals are used:
[0119] ㆍ H 80 is the height of the entire anode groove, which is generally between 0.25mm and 10mm.
[0120] ㆍ L 80 is the width of the anode groove, which is generally between 0.25mm and 10mm.
[0121] ㆍ H 82 is the height of each anode exclusion zone, which is generally configured between 0.25mm and 10mm.
[0122] ㆍ L 82 is the width of each anode exclusion area, which is generally configured between 0.25mm and 10mm.
[0123] Similarly, each cathode foil is also provided with different lines and columns of cathode unit objects (60, 60") provided in equal amounts to anode unit objects (60, 60').
[0124] In particular, as illustrated in FIG. 4, the structure of each cathode unit object (60) is substantially similar to the structure of each anode unit object (60'), that is, this cathode unit object (60) includes an exclusion area or non-coated area (72), a coated area (71), and a groove (70).
[0125] The exclusion area or non-coating area (72) of the cathode unit object (60) is understood to mean an area of the cathode foil (5e) that is not covered by the cathode layer (50) or is not covered by the cathode layer (50) and the electrolyte layer (30) or the separator layer (31).
[0126] The coated area (81) of the cathode unit object (60) is understood to mean an area of the cathode foil (5e) covered by the cathode layer (50) or covered by the cathode layer (50) and the electrolyte layer (30) or the separator layer (31).
[0127] The dimensions of the cathode exclusion area (72) are the same as the dimensions of the anode groove (80), and similarly, the dimensions of the anode exclusion area (82) are similar to the dimensions of the cathode groove (70).
[0128] When viewed from above, the cathode exclusion region (72) overlaps the upper part of the anode home (80) and the anode exclusion region (82) overlaps the upper part of the cathode home (70).
[0129] The only difference between the anode (60') and cathode (60") unit objects is that, on one hand, the cathode exclusion region (72) and the anode exclusion region (82) are inverted relative to each other. Meanwhile, the cathode groove (70) and the anode groove (80) are inverted relative to each other. In this way, when viewed from above, each anode exclusion region (82) is created in the continuation of each cathode groove (70), and each cathode exclusion region (72) is created in the continuation of each anode groove (80).
[0130] The cathode exclusion region (72) is a region that is free of any electrolyte material or separator and any cathode material. When created on a cathode foil, this cathode exclusion region (72) is created in such a way that it removes or prevents the deposition of any electrolyte material or separator and any cathode material, leaving at least a portion of the anode current collection substrate (10). In this manner, in the second longitudinal direction (XX") of the battery opposite to the first longitudinal direction (XX'), each cathode current collector substrate (40) protrudes from each cathode layer (50) and each layer (30) of the electrolyte material or the layer (31) of the separator impregnated with the electrolyte. When the current collector substrate is completely covered by the cathode layer (50), the substrate itself (50) is optionally covered by the electrolyte layer (30) or the separator layer (31), and a cathode exclusion region (72) can be created by laser ablation to locally remove the cathode layer (50) coated with the cathode layer (50) or the electrolyte layer (30) or the separator layer (31). The cathode exclusion region (72) can be created by local slot-die coating of the current collector substrate. Local slot-die coating of the current collector substrate allows for local deposition of, in particular, the cathode layer (50) on the substrate, and optionally subsequently It is covered with an electrolyte layer (30) or a separator layer (31) in the same way. A slot-die coating on the substrate that is symmetrical in the direction of movement of the substrate allows the uncoated area (72) to remain directly on the substrate; this reduces the number of steps in the method of manufacturing a unit on a cathode foil.
[0131] The cathode foil obtained after creating the home (70), the coated area (71), and the exclusion area (72) is referred to below as a cathode foil having a unit object (5e).
[0132] A stack (I) having at least one anode foil having a unit body (2e) and at least one cathode foil having a unit body (5e) is alternately formed to obtain at least one unit cell, and each unit cell comprises an anode current collection substrate (10), an anode layer (20), an electrolyte material layer (30) or a layer of a separator (31) impregnated with or subsequently impregnated with an electrolyte, a cathode layer (50), and a cathode current collection substrate (40).
[0133] The stack (I) comprises an alternating arrangement of at least one anode foil (2e) having a groove (80), an uncoated area (82), and a coated area (81), and at least one cathode foil (5e) having a groove (70), an uncoated area (72), and a coated area (71). Thus, at least one unit cell (100) is obtained that continuously comprises an anode current collector (10), an anode layer (20), an electrolyte material layer (30), and / or a separator layer (31), a cathode layer (50), and a cathode current collector (40).
[0134] This stack(I) is:
[0135] - In the first longitudinal direction (XX') of the battery, each anode current collector substrate (10) protrudes from each anode layer (20), each electrolyte material layer (30) and / or separator layer (31), each cathode layer (50), and each cathode current collector substrate layer (40), and
[0136] - In the second longitudinal direction (XX") of the battery opposite to the first longitudinal direction (XX'), each cathode current collector substrate (40) is manufactured to protrude from each anode layer (20), each electrolyte material layer (30) and / or separator layer (31), each cathode layer (50), and each anode current collector substrate layer (10).
[0137] When the above battery comprises a plurality of unit cells (100, 100', 100"), the unit cells (100, 100', 100") are arranged vertically, that is, overlapped along the frontal direction (ZZ) with respect to the main plane of the battery as shown in FIG. 10, preferably:
[0138] The above anode current collection substrate (10) is an anode current collection substrate (10) of two adjacent unit cells (100, 100', 100"), and
[0139] The cathode current collector (40) is configured to be the cathode current collector (40) of two adjacent unit cells (100, 100', 100").
[0140] It is assumed that the stack described above undergoes steps that ensure overall mechanical stability. These steps, known as such, specifically include a step of high-temperature pressing of different layers. As can be seen below, such a stack formed in this manner allows for the formation of individual batteries, the number of which is equal to the product of the number of lines (Y) and the number of columns (X).
[0141] To this end, referring to FIG. 5, three lines (L n-1 to L n+1 ) and 3 columns (R n-1 to R n+1 ) is illustrated. According to the present invention, the stack (I) has a plurality of lines, i.e., battery lines (L) below. n When including at least two lines of a unit entity also referred to as ), the first cutting pair (DX n and DX' n ) is at least one other line (L) of the battery formed from the integrated stack, as shown in FIGS. 16 and 17. n-1 , L n+1It is designed to separate a given line (Ln) of the battery (1000) from the stack. Each cut section formed in a penetrating manner, that is, extending through the entire height of the stack, is formed in a manner known to itself. Non-limiting examples include cutting by sawing, particularly cutting into cubes, guillotine cutting, or laser cutting. Furthermore, the area (90) of foil within the stack that does not form the battery is indicated by being filled with a solid line, while the volume of the groove is left blank and the volume of the exclusion area is gray.
[0142] As shown in FIG. 6, which is a larger enlarged view of one of the unit objects (60, 60') of FIG. 5, each cut section is typically formed in the longitudinal direction of the battery, the first longitudinal direction (XX'), or the second longitudinal direction (XX"). The cut section (DX n and DX' n ) are preferably made parallel to each other and preferably perpendicular to both the exclusion area (72, 82) and the groove (80, 70) of the unit object (60, 60', 60").
[0143] Referring again to FIG. 5, each final battery has two cut sections (DX) preferably parallel to each other at the front and rear. n and DX' n By ), and preferably on the right and left sides, a second pair of cut sections (DY) parallel to each other n and DY' n The boundary is determined by ).
[0144] In FIG. 5, the battery (1000) is a cutting line (D n , D' n ) along the cutting line (DY n , DY' n Once cut along ), it is hatched and depicted.
[0145] Under these conditions, with reference to FIG. 6, the following reference numbers are mentioned in the form of non-limiting examples:
[0146] - A distance (Dca) corresponding to the smallest distance between the first longitudinal plane (F6) of the battery, which includes at least one anode connection area (1002), and the first end plane (DYa). This distance (Dca) falls between 0.01 mm and 0.05 mm, and this distance (Dca) is L 82 / L 70 Understood as being smaller than or equal to;
[0147] - A distance (Dcc) corresponding to the smallest distance between the second longitudinal plane (F4) of the battery, which includes at least one cathode connection area (1006), and the second end plane (DY'a). This distance (Dcc) falls between 0.01 mm and 0.05 mm, and this distance (Dcc) is L 72 / L 80 It is understood as being smaller or equal to.
[0148] FIG. 7 is a cross-sectional view taken along the cutting line VII-VII extending through the battery. FIG. 7 illustrates an alternating arrangement of two anode foils having unit bodies (2e) and two cathode foils having unit bodies (5e). In the same figure, the following reference numerals are given: the grooves (70, 80), coated areas (71, 81), and exclusion areas (72, 82) of the unit bodies (60, 60') as illustrated in FIG. 6, and adjacent unit cells according to an advantageous embodiment of the present invention.
[0149] An anode foil having a unit body (2e) comprises an anode current collecting substrate (10) coated with an anode layer (20), which is optionally coated with an electrolyte layer (30) or subsequently coated with a separator layer (31) impregnated with an electrolyte. Each cathode foil having a unit body (5e) comprises a cathode current collecting substrate (40) coated with an active layer of cathode material (50), which is optionally coated with an electrolyte layer (30) or subsequently coated with a separator layer (31) impregnated with an electrolyte. To prevent any electrical contact between two active layers of opposite polarity, namely between the anode layer (20) and the cathode layer (50), at least one electrolyte layer (30) and / or at least one layer (31) of a separator impregnated with an electrolyte or subsequently impregnated with an electrolyte is discarded. FIG. 7 illustrates a unit cell (100) comprising an anode current collector (10), an anode layer (20), a layer (30) of at least one electrolyte material or a layer (31) of a separator impregnated with or subsequently impregnated with an electrolyte, a cathode layer (50), and a cathode current collector (40) in succession.
[0150] Advantageously, the anode current collection substrate (10) of the unit cell (100') may be adjacent to the anode current collection substrate (10) of the adjacent unit cell (100). Similarly, the cathode current collection substrate (40) of the unit cell (100) may be adjacent to the cathode current collection substrate (40) of the adjacent unit cell (100').
[0151] In one advantageous embodiment, the anode current collector (10) and each cathode current collector (40) can function as current collectors for two adjacent unit cells, particularly as illustrated in FIG. 7. As previously described, two sides of the anode (10) or each cathode (40) current collector are coated with an anode layer (20) or each cathode layer (50), optionally an electrolyte layer (30) or a separator layer (31), and are disposed on the anode layer (20) or on each cathode layer (50). This increases the production output of the battery.
[0152] As illustrated in FIG. 7, each anode foil having a unit object (2e) and each cathode foil having a unit object (5e) are arranged such that each cathode exclusion region (72) is formed as a continuation of each anode groove (80) and each anode exclusion region (82) is formed as a continuation of each cathode groove (70).
[0153] In the first longitudinal direction (XX'), each anode current collecting substrate (10) protrudes from each anode layer (20), a first end plane (DYa), which is defined by the first longitudinal end of each electrolyte material layer (30) or separator layer (31), each cathode layer (50) and each cathode current collecting substrate layer (40).
[0154] In the second longitudinal direction (XX") of the battery opposite to the first longitudinal direction (XX'), each cathode current collector substrate (40) protrudes from each anode layer (20), each electrolyte material layer (30) or a separator layer (31) impregnated with an electrolyte or subsequently impregnated with an electrolyte, each cathode layer (50), and each anode current collector substrate layer (10).
[0155] This is a particularly advantageous feature of the present invention because it prevents the presence of a short circuit at the side edge of the battery, prevents leakage current, and facilitates electrical contact in the anode connection area (1002) and the cathode connection area (1006).
[0156] In the cross-sectional view, the cathode exclusion region (72) overlaps the upper part of the anode groove (80), and the anode exclusion region (82) overlaps the upper part of the cathode groove (70).
[0157] Advantageously, after creating a stack of an anode foil having unit body (2e) and a cathode foil having unit body (5e), the stack (I) is integrated by thermal and / or mechanical treatment (this treatment may be a thermal compression treatment including the simultaneous application of pressure and high temperature). The thermal treatment of the stack that enables the battery to be assembled is advantageously performed at a temperature included between 50°C and 500°C, preferably at a temperature of less than 350°C. The mechanical compression of the stack of an anode foil having unit body (2e) and a cathode foil having unit body (5e) to be assembled is performed at a pressure included between 10 MPa and 100 MPa, preferably between 20 MPa and 50 MPa.
[0158] The production of an integrated stack of layers constituting a battery has just been described. Then, the stack (I) is produced in multiple lines, namely, the battery line (L) below. n When including at least two lines of a unit entity also called ), the first pair of cutting sections (DX n and DX' n ) is at least one other line (L) of the battery formed from the above integrated stack. n -1 , L n + 1) From the given line (L) of the battery (1000) nIt can be made to separate ). Each cut section, made in a through-way manner, that is, extending through the entire height of the stack, is made in a manner known in itself as indicated above. As shown in FIG. 17, the battery line (L n ) has 6 sides, that is:
[0159] - Two so-called end planes (FF1, FF2) facing each other, particularly parallel to each other, generally parallel to one or more anode current collection substrates (10), one or more anode layers (20), one or more layers (30) of an electrolyte material, one or more layers (31) of a separator combined with an electrolyte, one or more cathode layers (50), and one or more cathode current collection substrates (40),
[0160] - Two so-called sides (FF3, FF5) facing each other, particularly parallel to each other and parallel to the sides (F3, F5) of the battery (1000), and
[0161] - It has two so-called longitudinal planes (FF4, FF6) that face each other, particularly parallel to each other and parallel to the longitudinal planes (F4, F6) of the battery (1000).
[0162] When a separator is used as an electrolyte host matrix, the initial stack (I) consists of multiple batteries (L n When including the line of ) and the first pair of cut sections (DXn, DX'n) are given line (L of battery (1000) n ) at least one other line (L) of the battery (1000) formed by the above integrated stack n -1 , L n + 1) When made to be separated from, the line (L) of the previously obtained integrated stack or battery (100) n ) can be impregnated. A line (L) of a previously obtained integrated stack or battery (1000). nThe impregnation of the separator (31) can be produced by a phase having an ionic liquid containing lithium ions or lithium salts, such as a liquid electrolyte, so that the separator (31) is impregnated with the electrolyte.
[0163] After creating an integrated stack (I) impregnated with a phase having lithium ions optionally, a line (L) of this stack or battery (1000) n The battery cell is encapsulated by depositing an encapsulation system (95) to ensure protection of the battery cell from the atmosphere, as shown in FIG. 8. The encapsulation system must advantageously be chemically stable, able to withstand high temperatures, and impermeable to the atmosphere to function as a barrier layer.
[0164] The stack may be covered by an encapsulation system, said encapsulation system is:
[0165] - Optionally, preferably selected from parylene, parylene F, polyimide, epoxy resin, silicone, polyamide, sol-gel silica, organic silica and / or mixtures thereof, and a first dense and insulating cover layer deposited on a stack of anode and cathode foils; and
[0166] - Optionally, a second cover layer composed of an electrical insulating material deposited by atomic layer deposition on a stack of anode and cathode foils or on the first cover layer; and
[0167] - In a particularly advantageous way, preferably 10 -5 g / m 2 At least a third impermeable cover layer having a water vapor transmittance (WVTR) of less than .d, wherein the third cover layer is made of a ceramic material and / or low-melting-point glass, preferably glass having a melting point of less than 600°C deposited on a stack of anode and cathode foils or on the outer periphery of a first cover layer, and
[0168] This sequence of at least one second cover layer and at least one third cover layer can be repeated z times, where z ≥ 1, and can be deposited on the outer periphery of at least the third cover layer, and the last layer of the encapsulation system is preferably 10 -5 g / m 2 It is an impermeable cover layer having a water vapor permeability (WVTR) of less than .d, which is made of ceramic material and / or low-melting point glass.
[0169] This sequence can be repeated z times, where z ≥ 1. This has a barrier effect that increases as the value of z increases.
[0170] As a result, a rigid, impermeable encapsulation is created that prevents water vapor from passing through, in particular, at the interface between the encapsulation system and the contact member (see interface (A) in Fig. 11).
[0171] For the purposes of the present invention, the impermeable layer is 10 -5 g / m 2 It is defined as having a water vapor transmittance (WVTR) of less than .d. Water vapor transmittance can be measured using the method subject to U.S. Patent No. 7,624,621, which is described in the publication "Structural properties of UV-cured polysilazane gas barrier layers on polymer substrates" by A. Mortier et al. in Thin Solid Films 6+550 (2014) 85-89. Structural properties of ultraviolet cured polysilazane gas barrier layers on polymer substrates" It is listed in ”.
[0172] Typically, an optional first cover layer is selected from the group consisting of silicone (deposited, for example, by impregnation or by plasma-enhanced chemical vapor deposition from hexamethyldisiloxane (HMDSO)), epoxy resin, polyimide, polyamide, polypara-xylylene (also called poly(p-xylylene), but more widely known as parylene), and / or mixtures thereof. When the first cover layer is deposited, it protects sensitive elements of the battery from the environment. The thickness of the first cover layer is preferably 0.5 μm to 3 μm.
[0173] This first cover layer is particularly useful when the electrolyte and electrode layers of the battery are porous, as it acts as a planarization layer and also has a barrier effect. For example, this first layer can line a microporous surface open over the surface of the layer to block access thereto.
[0174] In this first cover layer, different parylene variants may be used. Parylene C, parylene D, parylene N (CAS 1633-22-3), parylene F, or a mixture of parylene C, D, N and / or F may be used. Parylene is a dielectric transparent semicrystalline material with high thermodynamic stability, excellent resistance to solvents, and very low permeability. Parylene also possesses barrier properties. Parylene F is preferred within the scope of the present invention.
[0175] This first cover layer is advantageously obtained from the condensation of gaseous monomers deposited by chemical vapor deposition (CVD) on the surfaces of the battery stack, which consequently results in an equiangular, thin, and uniform covering of all accessible surfaces of the stack. This first cover layer is advantageously rigid; it cannot be considered a flexible surface.
[0176] A second cover layer, also optional, is formed by an electrical insulating material, preferably an inorganic material. This is deposited by atomic layer deposition (ALD), PECVD, HDPCVD (high-density plasma chemical vapor deposition), or ICP CVD (inductively coupled plasma chemical vapor deposition) to obtain conformal covering of all accessible surfaces of the stack previously covered by the first cover layer. Layers deposited by ALD are mechanically very brittle and require a strong supporting surface to perform their protective role. The deposition of a brittle layer on a flexible surface leads to the formation of cracks, causing this protective layer to lose its integrity. Additionally, the growth of the layer deposited by ALD is affected by the properties of the substrate. On a substrate having zones of different chemical properties, a layer deposited by ALD will grow non-uniformly, which can cause the protective layer to lose its integrity. For this reason, when present, this optional second layer is preferably supported by the optional first layer, which ensures a chemically homogeneous growth substrate.
[0177] ALD deposition techniques are particularly suitable for covering surfaces with high roughness in a completely impermeable and conformal manner. They allow for the creation of a conformal layer free of defects such as holes (so-called "pinhole-free" layers) and exhibit excellent barrier properties. The water vapor permeability (WVTR) is extremely low. WVTR is used to evaluate the water vapor permeability of an encapsulation system. The lower the WVTR, the higher the impermeability of the encapsulation system. The thickness of this second layer is advantageously selected as a function of the desired level of impermeability to gas, i.e., the desired WVTR, and depends particularly on the deposition technique used, selected from ALD, PECVD, HDPCVD, and ICP CVD. The second cover layer may consist of ceramic materials, glassy materials, or glass-ceramic materials in the form of oxides, nitrides, phosphates, oxynitrides, or siloxanes, for example, of the Al2O3 or Ta2O5 type. This second cover layer preferably has a thickness between 10 nm and 10 μm, preferably between 10 nm and 50 nm.
[0178] This second cover layer, deposited on the first cover layer by ALD, PECVD, HDPCVD (High-Density Plasma Chemical Vapor Deposition), or ICP CVD (Inductively Coupled Plasma Chemical Vapor Deposition), first enables the structure to be impermeable, that is, to prevent water from moving into the object, and second, preferably, to protect the first cover layer composed of parylene F from the atmosphere, particularly air and moisture, and from heat exposure, thereby preventing their degradation. This second cover layer improves the life of the encapsulated battery.
[0179] The second cover layer can also be deposited directly on the stack of anode and cathode foils, that is, in the case where the first cover layer is not deposited.
[0180] This third cover layer may be formed by a ceramic material and / or low-melting-point glass, preferably glass having a melting point of less than 600°C, deposited around the anode and cathode foils or the stack of the first cover layer. The ceramic and / or glass material used for this third layer is advantageously selected from the following:
[0181] - Low melting point glass (generally > 600°C), preferably SiO2-B2O3; Bi2O3-B2O3, ZnO-Bi2O3-B2O3, TeO2-V2O5, PbO-SiO2,
[0182] - Oxides, Nitrides, Oxynitrides, Si x N y , SiO2, SiON, amorphous silicon or SiC.
[0183] These glasses can be deposited by molding or dip coating.
[0184] Ceramic materials are advantageously deposited by PECVD or preferably by HDPCVD or ICP CVD at low temperatures; these methods can deposit a layer having good impermeability.
[0185] As described above, the battery according to the present invention comprises an encapsulation system that is advantageously manufactured in the form of a continuous layer. This provides highly impermeable encapsulation on all sides of the battery. Furthermore, the overall dimensions of this encapsulation are very small, enabling the miniaturization required to produce microbatteries.
[0186] The description of the above encapsulation system shows significant differences, along with technical effects, when compared to the disclosure of U.S. Patent No. US 2018 / 212210 filed by Suzuki. In such prior art batteries, the resin in contact with the cell does not perform an impermeable encapsulation function. More specifically, this resin does not have the aforementioned permeable characteristics.
[0187] Additionally, this document submitted by Suzuki relates to a solid-state battery. Conversely, the battery according to the present invention cannot be entirely solid. In such a case, the longitudinal end of the battery is "open." In particular, as illustrated in FIG. 9, it is advantageous for the impermeable encapsulation system to be positioned to be in direct contact with the end of the electrolyte layer (30) or the separator layer (31) on the opposite longitudinal side (F4, F6). Consequently, this encapsulation system can "close" the pores (31) of each layer (30), which allows the nano-confined electrolyte inside the cell to be satisfactorily maintained. In an alternative embodiment not illustrated, this encapsulation system may be provided so as not to be in contact with other layers. However, such encapsulation preferably comes into direct contact with all components of the cell, except for the protruding substrate on the opposite longitudinal side of the stack.
[0188] In addition, the battery encapsulation system according to the present invention is advantageously electrically insulated. Accordingly, for the purposes of the present invention, the conductivity of such encapsulation system is advantageously 10 e-11 Sm -1 Less than, especially 10 e-12 Sm -1 It means that it is less than. This feature is advantageous because it prevents short circuits while allowing the opposite positive and negative connections to be reworked for compatibility with pick-and-place type electronic component placement machines. This feature is comparable to the disclosure of the aforementioned patent document filed by Suzuki, in which impermeability is provided by a metallic outer casing.
[0189] The stack coated in this way is then cut along the cutting lines (DYn and DY'n) by any suitable means to expose the anode connection area (1002) and the cathode connection area (1006) and obtain a unit battery as shown in FIG. 9.
[0190] As illustrated in FIGS. 9 and 10, the cut portion of the integrated and encapsulated stack along the cutting lines (DYn and DY'n) is formed as follows:
[0191] - Only each anode edge (1002') of each anode current collection substrate (10) is the first end plane (DY a It protrudes from ), and this first plane is defined by the first longitudinal end of each anode layer (20), each electrolyte material layer (30) and / or separator layer (31), each cathode layer (50), and each cathode current collector substrate layer (40) in the first longitudinal direction (xx') of the battery, and lies coplanar with the first longitudinal plane (F6),
[0192] - Only the cathode edge (1006') of each cathode current collection substrate (40) protrudes from the second end plane (DY'a), which is defined by the second longitudinal end of each anode layer (20), each electrolyte material layer (30) and / or separator layer (31), each cathode layer (50), and each anode current collection substrate layer (10) in the second longitudinal direction (XX") of the battery, and is positioned at the same height as the second longitudinal plane (F4), preferably the second longitudinal plane (F4) is opposite and parallel to the first longitudinal plane (F6),
[0193] Each anode edge (1002') defines an anode connection area (1002) and each cathode edge (1006') defines a cathode connection area (1006).
[0194] Contact members (97, 97', 97") (electrical contacts) are added where the cathode (1006) or each anode connection area (1002) is apparent. These contact areas are preferably placed on both sides of the battery stack to collect current (side current collectors). Contact members (97, 97', 97") are deposited on at least the cathode connection area (1006) and at least the anode connection area (1002), preferably on the surface of the coated and cut stack containing at least the cathode connection area (1006) and the surface of the coated and cut stack containing at least the anode connection area (1002) (see FIG. 11).
[0195] Accordingly, at least an anode connection area (1002), preferably at least a first longitudinal surface (F6) including at least an anode connection area (1002), more preferably at least a first longitudinal surface (F6) including at least an anode connection area (1002), and an end (97'a) of surfaces (F1, F2, F3, F5) adjacent to this first longitudinal surface (F6) is covered by an anode contact member (97') capable of creating electrical contact between the stack (I) and an external conductive element. Additionally, at least a cathode connection area (1006), preferably at least a second longitudinal face (F4) including at least a cathode connection area (1006), more preferably a second longitudinal face (F4) including at least a cathode connection area (1006), and an end (97"a) of a face (F1, F2, F3, F5) adjacent to the second longitudinal face (F4) is covered by a cathode contact member (97") capable of creating electrical contact between the stack (I) and an external conductive element.
[0196] Preferably, the contact member (97, 97', 97") is composed of a stack (I) of layers comprising a first electrical connection layer comprising a material filled with electrically conductive particles near the cathode connection zone (1006) and the anode connection zone (1002), preferably a material obtained by a sol-gel method filled with a polymer resin and / or electrically conductive particles and more preferably a graphite-filled polymer resin, and a second layer comprising a metal foil disposed on the first layer.
[0197] The first electrical connection layer allows the subsequent second electrical connection layer to be secured while providing "flexibility" in the connection without breaking the electrical contact when the electrical circuit is subjected to thermal and / or vibration stress.
[0198] The second electrical connection layer is a metal foil. This second electrical connection layer is used to provide continuous protection of the battery from moisture. Generally, for a given thickness of material, metal can produce a highly impermeable film that is more impermeable than ceramic-based films and much more impermeable than polymer-based films, which is typically not very impermeable to the passage of water molecules. By reducing the WVTR at the contact member, the calendar life of the battery is extended.
[0199] Advantageously, a third electrical connection layer containing conductive ink may be deposited on the second electrical connection layer; the purpose is to reduce WVTR and extend the battery life.
[0200] The contact members (97, 97', 97") allow electrical connections to be made alternately between positive and negative at each end. These contact members (97, 97', 97") allow for parallel electrical connections to be made between different battery elements. To this end, only a cathode connection can be made at one end and an anode connection can be used at the other end.
[0201] International patent application WO 2016 / 001584 describes a stack of multiple unit cells composed of alternately stacked anode and cathode foils (see FIG. 12), which is encapsulated in an encapsulation system (295) to protect the cells of the battery (2000) from the atmosphere. To obtain a unit battery having exposed anode (2002) and cathode (2006) connection areas, cutting of this encapsulated stack is performed along a cutting plane passing through an alternating sequence of electrodes and encapsulation systems. Due to the density difference between the electrodes and the encapsulation system of a conventional battery, cutting along this cutting plane poses a risk of tearing the encapsulation system near the cutting plane, causing a short circuit. In International patent application WO 2016 / 001584, during encapsulation, the encapsulation layer fills the gap of the foil stack supporting the U-shaped cut section. This encapsulation layer inserted into these gaps is thick and does not adhere well to the stack, which poses a risk that the encapsulation system (2095) will tear during subsequent cutting.
[0202] According to the present invention, this risk is eliminated by using a foil having the following unit entities:
[0203] - In the first longitudinal direction (XX'), each anode current collecting substrate (10) protrudes from the first end plane (DYa), and this first plane is defined by the first longitudinal end of each anode layer (20), each electrolyte material layer (30) or separator layer (31), each cathode layer (50) and each cathode current collecting substrate layer (40), and
[0204] - In the second longitudinal direction (XX") of the battery opposite to the first longitudinal direction (XX'), each cathode current collector substrate (40) protrudes from each anode layer (20), each layer (30) of an electrolyte material or a layer (31) of a separator impregnated with or subsequently impregnated with an electrolyte, each cathode layer (50), and each anode current collector substrate layer (10).
[0205] The hot-pressed mechanical structure of the unit is extremely rigid near the cutting point because the cathode and anode foils are alternately overlapped. The use of such a rigid structure, combined with the use of foil-bearing units, can reduce the number of defects during cutting and increase the cutting speed, thereby improving the battery's production output.
[0206] According to the present invention, the cutting portion (DY' n and DY n ) is formed through an anode foil having unit entities (2e) and a cathode foil having unit entities (5e) of similar density, so that a clean cut of high quality is produced. Also, the cut surface (DY' n , DY n In the vicinity of ), the presence of an anode material, an electrolyte, a separator impregnated or not impregnated with the electrolyte, a cathode, and an anode current collection substrate (10) without a cathode current collection substrate in the first longitudinal direction (XX'), as well as the presence of any anode material, an electrolyte, a separator impregnated or not impregnated with the electrolyte, a cathode, and an anode current collection substrate without a cathode current collection substrate in the second longitudinal direction (XX") of the cathode current collection substrate (40), prevents the risk of short circuits and leakage currents and facilitates electrical contact in the connection zones (1002, 1006). The anode connection zone (1002) and the cathode connection zone (1006) are preferably laterally opposite each other.
[0207] The unique structure of the battery according to the present invention prevents the presence of a short circuit in the longitudinal planes (F4, F6) of the battery, prevents leakage current, and facilitates electrical contact in the anode connection area (1002) and the cathode connection area (1006). More specifically, the absence of electrode material and electrolyte material in the longitudinal planes (F4, F6) of the battery, including the anode and cathode connection areas, prevents lateral leakage of lithium ions and facilitates the balancing of the battery; and the effective surfaces of the electrodes in contact with each other and separated by the first and second end planes (DYa, DY'a) are substantially the same as shown in FIGS. 7 to 10.
[0208] Alternatively, as illustrated in FIGS. 5 and FIGS. 16, a battery (1000') can be obtained according to the present invention. These batteries (1000') are the center (C) of the battery. 1000 The axis line (Z) parallel to the frontal axis line (ZZ) passing through ) 1000 It corresponds to a battery (1000) rotated 180° around the center. The batteries (1000, 1000') may have the same dimensions. The batteries (1000, 1000') may have the same or different longitudinal dimensions. Production of batteries (1000 and 1000') in the same stack optimizes the production output of the batteries while minimizing material debris (90).
[0209] A battery according to the present invention may be manufactured from a unit entity according to another alternative embodiment of the present invention. In a non-limiting example, as shown in FIG. 13, the coated area (71, 81) of the unit entity may be created by a slot-die coating on a current collection substrate (40, 10), which may be formed symmetrically in the direction of movement of the substrate. This reduces the number of steps in the method for manufacturing the unit entity on the cathode and anode foils by allowing the uncoated area (72, 82) to remain directly on the substrate. The exclusion area of each unit entity in the same row (R) may be common and may form an exclusion strip (82') (see FIG. 13 and 14).
[0210] As illustrated in FIG. 15, an additional battery (1000') can be obtained according to the present invention and according to an identical alternative embodiment of the present invention. This battery (1000') is the center (C) of the battery. 1000 An axis (Z) parallel to the frontal direction (ZZ) passing through ) 1000 It corresponds to a battery (1000) rotated 180° around the center. Production of batteries (1000 and 1000') in the same stack optimizes the production output of the battery while minimizing material debris (90).
[0211] In an alternative embodiment not shown, row (R n The exclusion area of each unit object of ) is the same row (R n It can be generated from an exclusion strip common to each unit of ), thus optimizing the production output of the battery while preventing the presence of material debris (90). Thus, the central part (4) of the alternating foil stack is entirely used to manufacture the battery according to the present invention.
[0212] FIGS. 18 to 20 illustrate other embodiments of the present invention. In these figures, any component similar to the component of the first embodiment is given the same reference number increased by 300.
[0213] The battery (1300) illustrated in FIG. 20 differs from the battery (1000) described above, particularly in that the battery comprises a single unit cell (400) covered by an encapsulation system (395). This single cell is arranged continuously from top to bottom in FIG. 20:
[0214] - Anode current collection board (310),
[0215] - Anode layer (320)
[0216] - A layer of separator impregnated with an electrolyte (331), which can be replaced with a layer of an electrolyte material as described above,
[0217] - Cathode layer (350), and
[0218] - Includes a cathode current collector substrate (340).
[0219] Referring to FIG. 18, different components of the battery are first placed on top of each other. This architecture is generally obtained by locally depositing on a substrate. A portion of the current collector is not covered by the deposit. The current collector substrates (310, 340) provided on the opposing end faces (F1, F2) are positioned so that their opposing ends protrude from the other layer on the opposing longitudinal faces (F4, F6). Then, as shown in FIG. 19, these components are covered by an encapsulation system (395).
[0220] Next, a cut is formed along the vertical lines (392, 393) shown in FIG. 19. As shown in FIG. 20, the aforementioned cut exposes the edges (311, 341) of each current collection substrate (310, 340). It should be noted that these edges are covered by sections (394 and 396) of the encapsulation system (395) that protrude longitudinally (XX) from two opposite directions.
[0221] FIG. 21 illustrates another embodiment of the present invention. In these figures, any component similar to the component of the first embodiment is given the same reference number increased by 400.
[0222] The battery (1400) of FIG. 21 includes a plurality of unit cells (500) arranged one by one below in the front direction (ZZ), similar to the battery (1000). In contrast to the battery (1000), the battery (1400) has an encapsulation system (495) similar to that described immediately above. In particular, the system (495) has a plurality of regions (494, 496) protruding in the direction XX. As with the battery (1300), these regions (494 and 496) are formed by creating cutouts (492, 493), which are indicated by vertical dotted lines and dashed lines in FIG. 21. These cutouts expose edges (411 and 441) belonging to different current collection substrates (410 and 440).
[0223] FIGS. 22 through 24 illustrate additional embodiments of the present invention to be compared with embodiments illustrated in FIGS. 18 through 20. In FIGS. 22 through 24, the same reference numbers are assigned, which are similar to the components of embodiments illustrated in FIGS. 18 through 20 and are increased by 200.
[0224] In a manner similar to the battery (1300), the battery (1500) illustrated in FIG. 24 comprises a single unit cell (600) covered by an encapsulation system (595). This single cell is arranged continuously from top to bottom in FIG. 24:
[0225] - Anode current collection board (510),
[0226] - Anode layer (520)
[0227] - A layer of separator impregnated with an electrolyte (531), which can be replaced with a layer of an electrolyte material as described above,
[0228] - Cathode layer (550), and
[0229] - Includes a cathode current collector substrate (540).
[0230] However, the battery (1500) differs from the battery (1300) in that the current collection substrates (510, 540) do not protrude longitudinally (XX) from other layers. Furthermore, the battery (1500) is equipped with two additional components, namely electrical connection members (560 and 570) provided on opposite ends of the cell (600). In particular, each of these connection members, which are identical to one another, generally has a thickness of less than 300 µm, preferably less than 100 µm.
[0231] Each connecting member is advantageously manufactured from an electrically conductive material, particularly a metallic material. This includes, in particular, aluminum, copper, or stainless steel. To improve weldability, these materials may be coated with a thin layer of gold, nickel, or tin.
[0232] Meanwhile, means of attachment between the connecting member (560) and the current collector (510), and between the connecting member (570) and the current collector (540), will now be described. Such means of attachment is typically formed by a conductive adhesive, in particular a graphite adhesive, or an adhesive filled with copper or aluminum metal nanoparticles. This conductive adhesive layer, not shown in FIG. 24, has a typical thickness of 0.1 micrometers to several micrometers. Alternatively, this conductive adhesive layer can be replaced by welding.
[0233] As illustrated in FIG. 22, each connecting member (560, 570) is positioned on each collector substrate (510, 540) in a longitudinally offset manner. More precisely, the first end of these connecting members forms a tab (562, 572), and the tab (562, 572) protrudes in two opposite directions from the longitudinal faces (F4 and F6) of the cell. Additionally, at the opposite end of these tabs, each connecting member is set back from the cell to define a shoulder (564, 574). This arrangement, which is an advantageous optional feature, makes it easy to visually distinguish the connecting members from other layers.
[0234] The cell (600) equipped with the connecting member is then covered with the encapsulation system. As shown in FIG. 23, the longitudinal face and side and shoulder (564, 574) of the cell are first covered with a partial encapsulation system (595'). Referring to FIG. 24, the end face of the connecting member is then covered to form the final encapsulation system (595). Finally, a cut is made similar to the cut (392, 393) of FIG. 19, although not shown. This exposes the edge (566, 576) of the connecting member. In this example, the encapsulation system is provided in two consecutive steps, and a single step may also be provided.
[0235] FIG. 25 illustrates an alternative embodiment of the embodiment shown in FIG. 22 through 24. In FIG. 25, components similar to those shown in FIG. 22 through 24 are given the same reference numbers increased by 100. As shown above, the electrical connection members (560, 570) protrude from the cell in two opposite directions in the longitudinal direction. In contrast, the electrical connection members (660, 670) of the battery (1600) shown in FIG. 25 all protrude in the same direction, that is, to the right in this figure.
[0236] The embodiments illustrated in FIGS. 18 through 20 and FIGS. 22 through 25 have specific advantages. More specifically, this relates to a "single cell" type battery that is highly suitable for specific applications requiring high energy density. Additionally, this architecture facilitates encapsulation.
[0237] Finally, the embodiments illustrated in FIGS. 22 through 25 also relate to the use of an electrical connection member having specific advantages. Thus, local deposition on the substrate is not required so that the entire surface of such a current collector substrate can be coated with an electrode material. Since a lateral offset is generated in the connection member, there is no longer a need for local deposition on the current collector, particularly as in the case of the embodiments of FIGS. 18, 19, and 20.
[0238] Referring to the embodiments of FIGS. 22 to 25, the present invention also relates to a battery (1500) comprising a stack formed by at least one unit cell, particularly a single unit cell (600), wherein each unit cell comprises, in succession, an anode current collector (510), an anode layer (520), a layer of at least one electrolyte material (530) and / or a layer of at least one separator impregnated with an electrolyte (531), a cathode layer (550), and a cathode current collector (540).
[0239] The stack and the battery have six sides, i.e.,
[0240] - Two so-called end planes (F1, F2) facing each other and generally parallel to the layer and the current collection substrate
[0241] - Two so-called longitudinal planes (F4, F6) facing each other and each including an anode and cathode connection region
[0242] - Includes two so-called sides facing each other,
[0243] The battery is characterized by further including two electrical connection members (560, 570) provided on opposite end surfaces of the stack, and a first end (562, 572) of each electrical connection member protruding longitudinally (XX) beyond each longitudinal surface (F4, F6) of the stack.
[0244] According to other features of this battery according to additional purposes of the present invention:
[0245] - The first end (562) of the connecting member (560) protrudes in the first direction beyond the first longitudinal plane (F4), whereas the first end (572) of the other connecting member (570) protrudes in the opposite direction from the other longitudinal plane (F6), and
[0246] - The first end (662, 672) of the two connecting members (660, 670) protrudes in the same direction beyond one identical longitudinal plane (F4), and
[0247] - Each electrical connection member is attached to each current collection substrate, particularly by a conductive adhesive, and
[0248] - None of the anode, cathode, and separator layers, nor any of the current collector substrates, protrude beyond the longitudinal plane of the stack, and
[0249] - On the opposite side of the protruding end, each electrical connection member defines the boundary of the shoulder (564, 574) together with the stack.
[0250] The method according to the present invention is particularly suitable for manufacturing all-solid-state batteries, that is, batteries in which the electrodes and electrolytes are solid and do not include a liquid phase impregnated in the solid phase.
[0251] The method according to the present invention is particularly suitable for manufacturing a battery considered to be in a semi-solid state, comprising at least one separator (31) impregnated with an electrolyte. The separator is preferably
[0252] - Porosity of more than 30%, preferably 35% to 50%, more preferably 40% to 50%, preferably mesoporous,
[0253] - Average diameter (D 50 It is a porous inorganic layer having pores of less than 50 nm.
[0254] The thickness of the separator is advantageously configured to be less than 10 μm, preferably 2.5 μm to 4.5 μm, to reduce the final thickness of the battery without compromising the characteristics of the battery. The pores of the separator are impregnated with an electrolyte, preferably an ionic liquid containing a lithium salt or a phase having lithium ions, such as a liquid electrolyte. In the porous, particularly mesoporous, "nano-confined" or "nano-entrapped" liquid can no longer escape. This is bound by a phenomenon referred to here as "absorption in the mesoporous structure" (which appears not to be described in the literature within the context of lithium-ion batteries), and the cell is placed under a vacuum. Thus, the battery is considered a semi-solid battery.
[0255] The battery according to the present invention may be a lithium-ion microbattery, a lithium-ion minibattery, or a high-power lithium-ion battery. In particular, it may be designed and sized to have a capacity of about 1 mAh or less (commonly known as a "microbattery"), a power greater than about 1 mAh or up to about 1 Ah (commonly known as a "minibattery"), or a capacity greater than about 1 Ah (commonly known as a "high-power battery"). Generally, microbatteries are designed to be compatible with microelectronic manufacturing methods.
[0256] Batteries for each of these three power ranges can be produced:
[0257] - Having "solid-state" type layers, i.e., without impregnated liquid or paste phases (the liquid or paste phases may be a lithium-ion conductive medium capable of acting as an electrolyte),
[0258] - or having mesoporous "solid-state" type layers impregnated with a liquid or paste-phase, generally a lithium-ion conductive medium, such a medium spontaneously penetrates the layer and no longer comes out, so this layer can be considered a semi-solid,
[0259] - or having impregnated porous layers (i.e., layers having a network of open holes that can be impregnated into a liquid or paste, imparting wetting properties to these layers).
Claims
Claim 1 A battery (1000) comprising at least one unit cell (100), wherein each unit cell (100) continuously comprises an anode current collection substrate (10), an anode layer (20), a layer (30) of at least one electrolyte material and / or a layer (31) of a separator impregnated with at least one electrolyte, a cathode layer (50), and a cathode current collection substrate (40); wherein the battery comprises a plurality of unit cells (100, 100', 100"), wherein one unit cell (100, 100', 100") is positioned below another, that is, overlapped along the frontal direction (ZZ) with respect to the main plane of the battery, wherein: ο the anode current collection substrate (10) is the anode current collection substrate (10) of two adjacent unit cells (100, 100', 100"), and ο the cathode current collection substrate (40) is the anode current collection substrate (10) of two adjacent unit cells A cathode current collector (40) of a cell (100, 100', 100"), wherein at least one unit cell or the unit cells (100, 100', 100") define a stack (I), and the stack (I) and the battery have six faces, namely: - two so-called end faces (F1, F2) that are opposite to each other and particularly parallel to each other and generally parallel to one or more anode current collectors (10), one or more anode layers (20), one or more layers of electrolyte material (30) or one or more layers of separators impregnated with electrolyte (31), one or more cathode layers (50), and one or more cathode current collectors (40); - two so-called side faces (F3, F5) that are opposite to each other and particularly parallel to each other; and - two so-called longitudinal faces (F4, F6) that are opposite to each other and particularly parallel to each other, and the first longitudinal of the battery A surface (F6) comprises at least one anode connection area (1002), and a second longitudinal surface (F4) of the battery comprises at least one cathode connection area (1006), wherein the anode connection area (1002) and the cathode connection area (1006) are laterally opposite each other, in a battery, - in the first longitudinal direction (XX') of the battery,A battery characterized in that each anode current collector substrate (10) protrudes from each anode layer (20), each electrolyte material layer (30) or electrolyte-impregnated separator layer (31), each cathode layer (50), and each cathode current collector substrate layer (40), and in a second longitudinal direction (XX") of the battery opposite to the first longitudinal direction (XX'), each cathode current collector substrate (40) protrudes from each anode layer (20), each electrolyte material layer (30) or electrolyte-impregnated separator layer (31), each cathode layer (50), and each anode current collector substrate layer (10). Claim 2 In claim 1, each anode current collection substrate (10) has a first end plane (DY a A battery characterized by protruding from ), wherein the first plane is defined by a first longitudinal end of each anode layer, each electrolyte material layer or separator layer, each cathode layer and each cathode current collector substrate layer. Claim 3 In claim 1, each cathode current collecting substrate (40) is a second end plane (DY' a A battery characterized by protruding from ), wherein the second plane is defined by a second longitudinal end of each anode layer, each layer of electrolyte material or separator, each cathode layer, and each anode current collection substrate layer. Claim 4 In claim 1, the encapsulation system covers at least a portion of the outer periphery of the stack (I), and the encapsulation system is 10 -5 g / m 2 A battery comprising at least one impermeable cover layer having a water vapor permeability (WVTR) of less than .d, wherein the encapsulation system is in direct contact with at least the layer (30) of the electrolyte material and / or the layer (31) of the separator impregnated with the electrolyte on each longitudinal surface (F4, F6). Claim 5 In claim 4, the battery is further characterized in that the encapsulation system also directly contacts the anode layer, the cathode layer, and the non-protruding current collection substrate on each longitudinal plane (F4, F6). Claim 6 In claim 4, the encapsulation system is electrically insulated, and the conductivity of the encapsulation system is 10 e-11 Sm -1 A battery characterized by being less than Claim 7 In claim 4, the encapsulation system (95) covers at least a portion of the end faces (F1, F2), side faces (F3, F5), and longitudinal faces (F4, F6) of the stack, such that in the first longitudinal direction (XX') of the battery, only the anode edge (1002') of each anode current collector (10) protruding from each anode layer (20), each electrolyte material layer (30) or separator layer (31), each cathode layer (50), and each cathode current collector substrate layer (40) is placed at the same height as the first longitudinal face (F6), and in the second longitudinal direction (XX") of the battery, each cathode of each cathode current collector substrate (40) protruding from each anode layer (20), each electrolyte material layer (30) or separator layer (31), each cathode of each cathode current collector substrate (40) protruding from each anode current collector substrate layer (20). A battery characterized in that an edge (1006') is placed at the same height as a second longitudinal plane (F4), the second longitudinal plane (F4) is opposite and parallel to a first longitudinal plane (F6), each anode edge (1002') defines an anode connection area (1002) and each cathode edge (1006') defines a cathode connection area (1006). Claim 8 In claim 4, the encapsulation system (95) comprises: - at least one impermeable cover layer made of a ceramic material and / or low-melting point glass, or - a cover layer selected from parylene, parylene F, polyimide, epoxy resin, silicone, polyamide, sol-gel silica, organic silica, and / or a mixture thereof, and deposited on at least a portion of the outer periphery of the stack (I); and - at least one impermeable cover layer made of a ceramic material and / or low-melting point glass and deposited on the cover layer, or - a cover layer composed of an electrical insulating material deposited by atomic layer deposition on at least a portion of the outer periphery of the stack (I); and - at least one impermeable cover layer made of a ceramic material and / or low-melting point glass and deposited on at least a portion of the outer periphery of the stack (I), wherein when the cover layer composed of the electrical insulating material is present, - the succession of the cover layer and the impermeable cover layer may be repeated z times, where z ≥ 1, and at least one A first cover layer deposited on the outer periphery of an impermeable cover layer, wherein - the last layer of the encapsulation system is an impermeable cover layer made of a ceramic material and / or low-melting-point glass, or - selected from parylene, parylene F, polyimide, epoxy resin, silicone, polyamide, sol-gel silica, organic silica, and / or a mixture thereof, and deposited on at least a portion of the outer periphery of the stack (I); - a second cover layer composed of an electrical insulating material deposited by atomic layer deposition on at least a portion of the outer periphery of the stack (I) or on the first cover layer; and - at least one third impermeable cover layer, wherein the third cover layer is made of a ceramic material and / or low-melting-point glass and is deposited on at least a portion of the outer periphery of the stack (I) or on the first cover layer, and when the second cover layer is present, - the sequence of the second cover layer and the third cover layer may be repeated z times, wherein z≥1, andA battery characterized by being deposited on the outer periphery of at least a third cover layer, wherein the last layer of the encapsulation system is an impermeable cover layer made of a ceramic material and / or low-melting-point glass. Claim 9 A battery according to claim 1, wherein a first longitudinal surface (F6) including at least an anode connection area (1002) is covered by an anode contact member (97'), and a second longitudinal surface (F4) including at least a cathode connection area (1006) is covered by a cathode contact member (97"), and said anode contact member (97') and cathode contact member (97") are capable of creating electrical contact between the stack (I) and an external conductive element. Claim 10 A battery according to claim 9, wherein each anode contact member (97') and cathode contact member (97") comprises: - a first electrical connection layer disposed on a first longitudinal plane (F6) comprising at least an anode connection area (1002) and a second longitudinal plane (F4) comprising at least a cathode connection area (1006), wherein the first electrical connection layer comprises a material filled with electrically conductive particles; and - a second electrical connection layer comprising a metal foil disposed on the first layer comprising the material filled with electrically conductive particles. Claim 11 In claim 1, a first longitudinal plane (F6) comprising at least one anode connection region (1002), and a first end plane (DY) defined by a first longitudinal end of each anode layer (20), each electrolyte material layer (30) and / or separator layer (31), each cathode layer (50), and each cathode current collection substrate layer (40). a The smallest distance (Dca) between ) is configured to be 0.01 mm to 0.5 mm and / or a second longitudinal plane (F4) comprising at least one cathode connection region (1006), and a second end plane (DY') defined by the second longitudinal end of each anode layer (20), each electrolyte material layer (30) and / or separator layer (31), each cathode layer (50), and each anode current collection substrate layer (10). a A battery characterized in that the smallest distance (Dcc) between ) is composed of 0.01 mm to 0.5 mm. Claim 12 A method for manufacturing at least one battery (1000), wherein each battery comprises at least one unit cell (100), and each unit cell (100) comprises an anode current collection substrate (10), an anode layer (20), a layer (30) of at least one electrolyte material and / or a layer (31) of at least one separator impregnated with an electrolyte, a cathode layer (50), and a cathode current collection substrate (40) in succession, wherein the battery (1000) comprises a plurality of unit cells (100, 100', 100"), wherein one unit cell (100, 100', 100") is placed below another, that is, overlapped along the frontal direction (ZZ) with respect to the main plane of the battery: ο the anode current collection substrate (10) is the anode current collection substrate (10) of two adjacent unit cells (100, 100'), and ο the cathode current collection The substrate (40) is a cathode current collection substrate (40) of two adjacent unit cells (100, 100'), and the at least one unit cell (100) or unit cells (100, 100', 100") defines a stack (I), and the stack (I) and the battery (1000) have six faces, namely: - two so-called end faces (F1, F2) that are opposite to each other, particularly parallel to each other, and generally parallel to one or more anode current collection substrates (10), one or more anode layers (20), one or more layers of electrolyte material (30) or one or more layers of separator impregnated with electrolyte (31), one or more cathode layers (50), and one or more cathode current collection substrates (40); - two so-called side faces (F3, F5) that are opposite to each other, particularly parallel to each other; and - two so-called longitudinal faces (F4, The battery has F6), wherein the first longitudinal surface (F6) of the battery includes at least one anode connection area (1002), and the second longitudinal surface (F4) of the battery includes at least one cathode connection area (1006), and the anode connection area (1002) and the cathode connection area (1006) are laterally opposite each other.- In the first longitudinal direction (XX') of the battery, each anode current collector substrate (10) protrudes from each anode layer (20), each electrolyte material layer (30) or layer of separator impregnated with electrolyte (31), each cathode layer (50), and each cathode current collector substrate layer (40), and - In the second longitudinal direction (XX") of the battery opposite to the first longitudinal direction (XX'), each cathode current collector substrate (40) protrudes from each anode layer (20), each electrolyte material layer (30) or layer of separator impregnated with electrolyte (31), each cathode layer (50), and each anode current collector substrate layer (10), and the manufacturing method comprises: (i) at least one anode current collector substrate foil (10) having a groove (80), an uncoated area (82), and an area (81) coated with an anode layer (20), wherein the anode (ii) a step of providing an anode current collecting substrate foil (10), wherein the layer (20) may or may not be coated with a layer (30) of an electrolyte material or a layer (31) of a separator, and is hereinafter referred to as an anode foil (2e); (iii) a step of providing at least one cathode current collecting substrate foil (40) having a groove (70), an uncoated area (72), and an area (71) coated with a cathode layer (50), wherein the cathode layer may or may not be coated with a layer (30) of an electrolyte material or a layer (31) of a separator, and is hereinafter referred to as a cathode foil (5e); (iii) a step of providing at least one unit cell comprising the anode current collecting substrate (10), an anode layer (20), at least one layer (30) of an electrolyte material or a layer (31) of a separator, a cathode layer (50), and a cathode current collecting substrate (40) in succession. To obtain, a step of generating an alternating stack (I) comprising at least one anode foil (2e) having a groove (80), an uncoated area (82), and a coated area (81), and at least one cathode foil (5e) having a groove (70), an uncoated area (72), and a coated area (71), wherein, in the first longitudinal direction (XX') of the battery,A step of creating the stack (I), wherein each anode current collector substrate (10) protrudes from each anode layer (20), each electrolyte material layer (30) and / or separator layer (31), each cathode layer (50), and each cathode current collector substrate layer (40), and wherein, in a second longitudinal direction (XX") of the battery opposite to the first longitudinal direction (XX'), each cathode current collector substrate (40) protrudes from each anode layer (20), each electrolyte material layer (30) and / or separator layer (31), each cathode layer (50), and each anode current collector substrate layer (10); (iv) a step of heat-treating and / or mechanically compressing the stack (I) of alternating foils obtained in step (iii) to form an integrated stack; (v) optionally, a given line (L, of the battery (1000). n ) at least one other line (L) of the battery (1000) formed from the integrated stack above n-1 , L n+1 A step of forming a first pair of cutting sections (DXn, DX'n) to be separated from ), (vi) optionally, so that the layer (31) of the separator is impregnated with an electrolyte, the integrated stack obtained in step (iv) or the line (L) of the battery (1000) obtained in step (v) when step (v) is performed. n (vii) a step of impregnating ) into a phase having lithium ions, such as an ionic liquid containing a lithium salt or a liquid electrolyte, (vii) forming a second pair of cut portions (DYn, DY'n) so as to expose the anode edge (1002') of each anode current collection substrate (10) protruding from each anode layer (20), each electrolyte material layer (30) or separator layer (31), each cathode layer (50), and each cathode current collection substrate layer (40) in the first longitudinal direction (XX') of the battery, such that each anode edge (1002') defines at least one anode connection region (1002), and in the second longitudinal direction (XX") of the battery, each anode layer (20), each electrolyte material layer (30) or separator layer (31), each cathode layer (50), and each anode current collection substrate The method includes the step of forming the second pair of cut portions by exposing the cathode edge (1006') of each cathode current collection substrate (40) protruding from the layer (10) so that each cathode edge (1006') defines at least one cathode connection area (1006), wherein the second pair of cut portions (DYn, DY'n) are such that, when step (v) is performed, the given battery is a line (L) of the battery (1000). n A manufacturing method that enables separation from at least one other battery formed from ). Claim 13 In claim 12, if step (vi) is performed, after step (vi), or if step (vi) is not performed and step (v) is performed, after step (v), or if steps (vi) and (v) are not performed, after step (iv), and, before step (vii), (viii) line (L of the integrated stack or battery (1000). n A step of encapsulating ) is performed, and the end faces (F1, F2) of the stack or the line (L) of the battery is encapsulated. n At least a portion of the cross-sectional surface (FF1, FF2), side surface (F3, F5, FF3, FF5) and longitudinal surface (F4, F6, FF4, FF6) of the battery is covered by an encapsulation system (95), so that in the first longitudinal direction (XX') of the battery, only the anode edge (1002') of each anode current collection substrate (10) protruding from each anode layer (20), each electrolyte material layer (30) or separator layer (31), each cathode layer (50), and each cathode current collection substrate layer (40) is positioned at the same height as the first longitudinal surface (F6, FF6), and in the second longitudinal direction (XX") of the battery, protruding from each anode layer (20), each electrolyte material layer (30) or separator layer (31), each cathode layer (50), and each anode current collection substrate layer (10) A manufacturing method characterized by each cathode edge (1006') of each cathode current collection substrate (40) being positioned at the same height as the second longitudinal plane (F4, FF4), so that the second longitudinal plane (F4, FF4) is opposite and parallel to the first longitudinal plane (F6, FF6), and each anode edge (1002') defining an anode connection area (1002) and each cathode edge (1006') defining a cathode connection area (1006). Claim 14 In claim 13, the encapsulation system (95) is: - made of a ceramic material and / or low-melting-point glass, and the line (L) of the stack (I) or battery (1000) n It comprises at least one third impermeable cover layer deposited on at least a portion of the outer periphery of ), or - selected from parylene, parylene F, polyimide, epoxy resin, silicone, polyamide, sol-gel silica, organic silica, and / or mixtures thereof, and a line (L) of the stack (I) or battery (1000). n At least one cover layer deposited on at least a portion of the outer periphery of ), and - comprising at least one impermeable cover layer made of a ceramic material and / or low-melting point glass and deposited on said cover layer, or - comprising a cover layer composed of an electrical insulating material deposited by atomic layer deposition on at least a portion of the outer periphery of said stack (I), and - comprising at least one impermeable cover layer made of a ceramic material and / or low-melting point glass, additionally, the sequence of the at least one cover layer composed of said electrical insulating material and said at least one impermeable cover layer may be repeated z times, wherein z ≥ 1, and the last layer of said encapsulation system is an impermeable cover layer made of a ceramic material and / or low-melting point glass, deposited on the outer periphery of at least one impermeable cover layer, or - at least one the selected from parylene, parylene F, polyimide, epoxy resin, silicone, polyamide, sol-gel silica, organic silica, and / or a mixture thereof, and deposited on at least a portion of the outer periphery of said stack (I). A method of manufacturing comprising: 1 cover layer; - a second cover layer composed of an electrical insulating material deposited by atomic layer deposition on the first cover layer; and - at least one third opaque cover layer made of a ceramic material and / or low-melting-point glass, wherein, additionally, when the second cover layer is present, - a sequence of the second cover layer and the third cover layer may be repeated z times, where z ≥ 1, and is deposited on the outer periphery of at least one third cover layer; and - the last layer of the encapsulation system is an opaque cover layer made of a ceramic material and / or low-melting-point glass. Claim 15 In any one of claims 12 to 14, after step (vii), at least a first longitudinal surface (F6) comprising at least an anode connection area (1002) is covered by an anode contact member (97') capable of creating electrical contact between the stack (I) and an external conductive element, and at least a second longitudinal surface (F4) comprising at least a cathode connection area (1006) is covered by a cathode contact member (97") capable of creating electrical contact between the stack (I) and an external conductive element, and the manufacture of the anode contact member (97') and the cathode contact member (97") comprises: - a step of depositing a first electrical connection layer made of a material filled with electrically conductive particles on at least a first longitudinal surface (F6) comprising at least an anode connection area (1002) and at least a second longitudinal surface (F4) comprising at least a cathode connection area (1006), wherein the first A manufacturing method comprising the steps of: depositing a first electrical connection layer, preferably made of a material obtained by a sol-gel method filled with a polymer resin and / or electrically conductive particles; and depositing a second electrical connection layer on the first layer, the second electrical connection layer comprising a metal foil disposed on the first electrical connection layer. Claim 16 A method of manufacturing according to claim 12 or 13, wherein, where step (v) is performed, the cut portions formed in step (v) and / or step (vii) are formed by laser ablation, or where, where step (v) is performed, all cut portions formed in step (v) and / or step (vii) are formed by a laser. Claim 17 A battery (1500) comprising a stack formed by at least one unit cell, particularly a single unit cell (600), wherein each unit cell comprises an anode current collection substrate (510), an anode layer (520), a layer of at least one electrolyte material (530) and / or a layer of at least one separator impregnated with electrolyte (531), a cathode layer (550), and a cathode current collection substrate (540) in succession, and the stack and the battery comprises six faces, namely: • two so-called end faces (F1, F2) facing each other and generally parallel to the layers and the current collection substrates; • two so-called longitudinal faces (F4, F6) facing each other and each comprising an anode connection area and a cathode connection area; and • two so-called side faces facing each other; wherein the battery comprises two electrical connection members (560, 570) provided on the opposing end faces of the stack, and each longitudinal face (F4, A battery characterized by further including a first end (562, 572) of each electrical connection member protruding longitudinally (XX) beyond F6). Claim 18 A battery according to claim 17, characterized in that a first end (562) of one connecting member (560) protrudes in a first direction beyond a first longitudinal plane (F4), while a first end (572) of another connecting member (570) protrudes in the opposite direction from another longitudinal plane (F6). Claim 19 A battery according to claim 17, characterized in that the first end (662, 672) of the two connecting members (660, 670) protrudes in the same direction beyond one same longitudinal plane (F4). Claim 20 A battery according to claim 17, characterized in that each electrical connection member is attached to each current collection substrate, particularly by a conductive adhesive. Claim 21 A battery according to claim 17, characterized in that none of the anode, cathode, and separator layer, as well as the current collector substrate, protrude beyond the longitudinal plane of the stack. Claim 22 A battery according to claim 17, characterized in that, opposite to the protruding end, each electrical connection member defines the shoulder (564, 574) together with the stack. Claim 23 In claim 8, the third impermeable cover layer made of a ceramic material and / or low-melting-point glass comprises low-melting-point glass having a melting point of less than 600°C, a battery. Claim 24 In claim 8, the third impermeable cover layer is 10 -5 g / m 2 A battery having a water vapor permeability (WVTR) of less than .d. Claim 25 In claim 8, the impermeable cover layer, which is the last layer of the encapsulation system, is 10 -5 g / m 2 A battery having a water vapor permeability (WVTR) of less than .d. Claim 26 In claim 10, the battery, wherein the material filled with the electrically conductive particles is a graphite-charged polymer resin.
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