Electrical energy storage device featuring an improved architecture, manufacturing process and corresponding energy consumption set

Abstract

ELECTRICAL ENERGY STORAGE DEVICE WITH AN IMPROVED ARCHITECTURE, CORRESPONDING MANUFACTURING METHOD AND ENERGY CONSUMPTION DEVICE This device, of the battery (1), capacitor or supercapacitor type, comprises an energy storage module (2) having first electrodes (3a – 3n) and second electrodes (4a – 4n) alternating with interposition of separators, each electrode comprising a main body (31; 41), a secondary body (32; 42) and a space (33; 43) free at least of any electrode material and / or any current collector substrate, as well as an electrical connection support (5) and electrical contact members (60, 61) suitable for ensuring the electrical connection between each electrode (3, 4) and connection regions of the support.According to the invention, the electrical energy storage module (2) rests, by one of its lateral faces (23), on a front face (51) of the support, the various electrodes (3, 4) being in contact, by one of their longitudinal edges, with a respective contact member (60, 61). Given the positioning of the storage module, the current from the electrodes can be collected very satisfactorily, regardless of the size of this module. Moreover, the electrical contact is planar. Finally, the impregnation can be carried out after the storage module is mounted on its support. Figure 3.

Description

Title of the invention: ELECTRICAL ENERGY STORAGE DEVICE HAVING A PER ARCHITECTURE CORRESPONDING MANUFACTURING METHOD AND ENERGY CONSUMPTION ASSEMBLY Technical field of the invention

[0001] The present invention relates to devices for storing electrical energy. It relates first of all to a new architecture of these devices, which in particular gives them improved power. The invention also relates to a method for manufacturing these electrical energy storage devices. Finally, it relates to an electrical energy consuming assembly, which is equipped with such a device for storing this electrical energy. State of the art

[0002] The electrical energy storage devices, as targeted by the invention, are intended to be associated with electronic circuits. These devices are then capable of ensuring different functions: we will cite in particular the power supply of these circuits, the communication with autonomous devices, or even the emergency power supply ("power back up") of real-time clocks. For the purposes of the invention, such an electrical energy storage device designates in particular a battery, in particular in thin layers, in particular with lithium, sodium or potassium ions. We will also cite the different types of capacitors and supercapacitors.

[0003] Such an electrical energy storage device firstly comprises an electrical energy storage module, typically formed by an alternating stack of different layers of electrodes, which are separated by an electronic insulating separator. In the case of a battery, there is a succession of electrodes of opposite polarities (anodes and cathodes) while the separator is capable of conducting solvated ions in the electrolyte in contact with the anodes and the cathodes. In the case of certain capacitors and supercapacitors, there is a succession of electrodes of the same polarity while the separator is capable of conducting solvated ionic charge carriers coming from the electrolyte, under the influence of an electric field. Finally, in the case of other capacitors and supercapacitors, there is a succession of current collectors which will also be called "electrodes" in the context of the present invention.

[0004] Generally speaking, most of the stacks as described above, belonging to both batteries and capacitors and supercapacitors, must be encapsulated to be durable. Indeed, some of the active materials in lithium, sodium, or potassium ion batteries are very sensitive to air and water vapor. In particular, mobile lithium ions react spontaneously with traces of water to form LiOH, leading to calendar aging of the batteries. The same type of reaction is observed with mobile sodium and potassium ions.

[0005] Not all insertion materials and electrolytes conducting lithium, sodium or potassium ions are reactive upon contact with moisture. For example, Li4Ti50i2 does not deteriorate upon contact with the atmosphere or traces of water. On the other hand, as soon as it is charged with lithium in the form Li4+xTi50i2 with x>0, then the excess lithium inserted (x) is, for its part, sensitive to the atmosphere and reacts spontaneously with the traces of water to form LiOH. This reacted lithium is then no longer available for storing electricity, leading to a loss of battery capacity.

[0006] The market demands a lifespan of more than 10 years. To avoid exposure of the active materials of the lithium ion (or sodium or potassium) battery to air and water and prevent this type of aging, it is essential to protect it with an encapsulation system that guarantees this lifespan. Many encapsulation systems for thin-film batteries are described in the literature.

[0007] A first solution consists of integrating the aforementioned stack into a metal case; these devices are called button batteries. Metals are in fact among the most impermeable materials, whether with regard to permeation to water or to atmospheric gas. However, such encapsulation technologies are bulky so that they lead to the production of components, which do not meet the miniaturization requirements.

[0008] In order to reduce manufacturing costs, it is particularly preferred to be able to mount electronic components automatically on electronic circuits. In particular, the components must be compatible with so-called “SMD” (Surface Mounted Components) processes. In other words, they must be capable of being mounted using robotic “pick and place” processes, then assembled by reflow or “solder reflow”. These SMD processes advantageously use QFN (Quad Fiat No-Leads) type packages, or DFN (Dual Fiat No-Leads) type packages.

[0009] In order to produce components which are compatible with CMS processes, which are highly compact and which make it possible to achieve the expected sealing levels, the applicant has proposed different types of architectures.

[0010] First of all, we will cite document FR-A-3 068 830, which describes a system encapsulation system for a battery comprising an alternating stack of anodes and cathodes. This system is formed by three successive layers, the first of which is composed of an electrically insulating material deposited by ALD (Atomic Layer Deposition). A second covering layer, comprising parylene, is arranged on the first covering layer, while a third covering layer is deposited on this second layer so as to protect it, in particular from oxygen.

[0011] Furthermore, WO 2021 / 130 688 provides for the stack formed by the anodes and the cathodes to cooperate with an electrical connection support. The latter has two mutually distant connection regions, which are insulated by an intermediate sole. The stack lies flat on the support, namely that these constituent layers are parallel to the planes of the support. In order to ensure the electrical connection between the stack and the aforementioned connection regions, conductive adhesive pads are provided on the opposite lateral faces of the stack.

[0012] The solution described in the latter document provides numerous advantages, in particular in that it allows a large number of energy storage devices to be manufactured simultaneously. Furthermore, it allows a convenient and reliable association between this energy storage device and an energy consuming assembly, while ensuring satisfactory sealing.

[0013] This solution, however, has specific drawbacks. Thus, in the case of a very thick stack, it is necessary to use a significant quantity of conductive glue in order to ensure the connection as described above. In addition to the glue consumption, this increases the overall footprint of the component, while increasing the risks of loss of electrical contact.

[0014] Such a very thick stack does not lend itself conveniently to the production of through passages allowing the introduction of conductive means, according to the teaching of WO-A-2021 / 130697 in the name of the applicant. The storage device, in particular of the battery type, may thus have a limiting thickness, beyond which it can no longer be passed through.

[0015] Furthermore, in order to ensure contact with all the cells forming the stack, it is necessary to use polymers, the electrochemical stability of which is however often limited. However, these polymers are incompatible with cathodes operating at high potentials, typically greater than 4.5 V.

[0016] Finally, the mounting of the elementary stack on the support is a costly operation, which does not guarantee a totally satisfactory quality of electrical contact. In fact, the stack must be impregnated using the liquid electrolyte before being mounted on the support. All the steps, allowing this mounting, must therefore be carried out in an anhydrous room, which is particularly costly. elsewhere we find the presence of liquid residue at the level of the bonding interface, between the terminations and the conductive glue, which makes the quality of the contact sometimes insufficient and random.

[0017] The present invention aims to remedy at least in part certain drawbacks of the prior art mentioned above.

[0018] It aims in particular to propose an electrical energy storage device, the specific architecture of which gives it excellent reliability, associated with low contact resistances as well as improved efficiency compared to the prior art.

[0019] The invention also aims to propose such an electrical energy storage device which, while being very compact, lends itself easily to mass production processes.

[0020] It also aims to propose such an electrical energy storage device, which can be manufactured using a less expensive method than in the prior art. Objects of the invention

[0021] At least one of the above objectives is achieved by a first object of the invention, which is an electrical energy storage device, in particular of the battery (1), capacitor or supercapacitor type, comprising

[0022] - an energy storage module (2) comprising

[0023] - at least one first electrode (3a - 3n) and at least one second electrode (4a - 4n), which are arranged one above the other in an alternating manner,

[0024] - at least one electronic separator, each separator separating a first electrode and a second adjacent electrode,

[0025] both the first electrode and the second electrode each comprising a main body (31; 41), a secondary body (32; 42) and a so-called free space (33; 43), which is free at least of any electrode material and / or any current collector substrate, each free space separating a respective main body and secondary body

[0026] - this storage module comprising so-called opposite front faces (21, 22), which are parallel to the planes of the different electrodes, as well as the so-called lateral faces (23 - 26), which are in particular opposed two by two,

[0027] - an electrical connection support (5), made at least partly of a material conductor, comprising a first electrical connection region (58) and a second electrical connection region (59) which are electrically insulated from each other,

[0028] - a first electrical contact member (60), capable of ensuring the electrical connection between each first electrode (3) and the first electrical connection region (58),

[0029] - a second electrical contact member (61), capable of ensuring the electrical connection between each second electrode (4) and the second electrical connection region (59),

[0030] said electrical energy storage device being characterized in that

[0031] - the electrical energy storage module (2) rests, by one of its faces lateral, called lateral contact face (23), on a front face (51) called reception, of the electrical connection support,

[0032] - the different first electrodes being in contact, by one of their long edges tudinal, with the first contact organ (60),

[0033] - the different second electrodes being in contact, by one of their long edges tudinal, with the second contact organ (61).

[0034] According to other characteristics of this device, taken in isolation or according to any technically compatible characteristics:

[0035] - the different main bodies (31) of the first electrodes (3) are in contact with the first contact member (60), while the different main bodies (41) of the second electrodes are in contact with the second contact member (61);

[0036] - the main plane (P5) of the support (5) and the main median plane (P2) of the module of storage (2) are mutually oblique, in particular mutually perpendicular;

[0037] - each of the free spaces (33, 43) opens, by a first end (331, 431), on the front receiving face (51) of the support and, by a second end (332, 432), opposite said front receiving face;

[0038] - said first end (331, 431) of each free space (33, 43) is located at distance from the electrical contact member (60, 61) adjacent to this first end;

[0039] - each electrical contact member (60, 61) is capable of providing an additional function mechanical connection between the storage module and the support;

[0040] - the electrical contact member is made of a conductive adhesive material;

[0041] - the electrical contact member has a thickness (e60) of less than 100 pm (microns);

[0042] - the free space (2033) of each first electrode, or of each second electrode, comprises a through branch (2330) connecting the longitudinal edges of said electrode as well as an auxiliary branch (2331) connecting the through branch with the transverse edge (2304) opposite said electrode, the auxiliary branch separating the main body (2031) from a so-called tertiary body (2035) while the through branch separates the secondary body (2032) from both the main body and the tertiary body;

[0043] - each first electrode is a first polarity electrode, while each second electrode is a second polarity electrode;

[0044] - this device is a battery, the separator being made of an electrically insulating material electronic but ionic conductor, the energy storage module further comprising a liquid electrolyte impregnating at least part of the electrodes and / or the se- parator;

[0045] - this device is a pseudo-capacitor, a hybrid ion supercapacitor of lithium, a sodium ion hybrid supercapacitor, a potassium ion hybrid supercapacitor, lithium ion batteries, sodium ion batteries, potassium ion batteries, the separator being made of an electronic insulating material but conducting electrical charges;

[0046] - this device is a capacitor, preferably chosen from a capacitor of Metal-Insulator-Metal (MIM) type and multilayer capacitors, each first electrode and each second electrode being a current collector;

[0047] - this device further comprises a mechanical protection system (707), ensuring mechanical protection at least with respect to the storage module;

[0048] - this device further comprises an encapsulation system (7; 607), in particular confused with the mechanical protection system, the encapsulation system ensuring protection with regard to the sealing of both the storage module and the electrical connection support;

[0049] - said encapsulation system (7) covers the opposite front faces (21, 22) of the storage module, the lateral face (24) of the storage module opposite the lateral contact face, the two other lateral faces (25, 26) of the storage module, at least in part the first electrical contact member (60), at least in part the second electrical contact member (61), as well as at least in part the receiving face (51) of said electrical connection support (5);

[0050] - this device further comprises a mechanical stiffening system (8), re covering the encapsulation system opposite the electrical connection support (5).

[0051] The invention also relates to a method of manufacturing a device such as above,

[0052] said method comprising:

[0053] - the relative positioning of the energy storage module (2) and the support of electrical connection (5), substantially in the final position they must adopt,

[0054] - the electrical connection of each first electrode (3) with the first electrical connection region (58) of the support,

[0055] - the electrical connection of each second electrode (4) with the second electrical connection region (59) of the support,

[0056] - possibly impregnating the energy storage module by means of the electrolyte,

[0057] - possibly the coating of the encapsulation system (7).

[0058] According to other characteristics of this process, taken in isolation or according to any technically compatible characteristics:

[0059] - this method comprises

[0060] - the provision of a blank (2') not impregnated with electrolyte, said blank being intended to form the energy storage module,

[0061] - the relative positioning of the blank and the electrical connection support,

[0062] - impregnation of the blank by means of the electrolyte, so as to form the energy storage module;

[0063] - at least a portion (509) of said electrolyte is introduced via the second end (332, 432) of said free spaces;

[0064] - the blank is impregnated by making the electrolyte flow by gravity (G509, H509);

[0065] The invention finally relates to an electrical energy consuming assembly (1000) comprising a body (1002), an energy consuming element (1004) as well as at least one electrical energy storage device (1) above, said electrical energy storage device (1) being capable of supplying electrical energy to said electrical energy consuming element (1004), and said electrical connection support (5) of said electrical energy storage device being fixed to said body.

[0066] According to other advantageous characteristics of this energy-consuming assembly:

[0067] - it comprises at least two energy storage devices which are placed on a single electrical connection support and are connected in series and / or in parallel, said at least two energy storage devices being advantageously covered by means of a single encapsulation system, and / or a single mechanical protection system;

[0068] - it includes an additional electronic component, placed on a single electrical connection support with the electrical energy storage device, this electronic component and this energy storage device being advantageously covered by means of a single encapsulation system, and / or a single mechanical protection system. Figures

[0069] The invention will be described below, with reference to the appended drawings, given solely as non-limiting examples, in which:

[0070] [Fig-1] is a front view illustrating a battery, forming a storage device of electrical energy according to a first embodiment of the invention.

[0071] [Fig.2] is a side view schematically illustrating a support and a module of electrical energy storage belonging to the battery shown in the previous figure.

[0072] [Fig.3] is a perspective view illustrating in an exploded and cut-away manner, some of the constituent elements of the battery of the previous figures.

[0073] [Fig.4] is a perspective view illustrating on a larger scale, according to zoom IV in [Fig.3], the contact between a support and main bodies of different anodes belonging to the battery of the previous figures.

[0074] [Fig.5] is a perspective view illustrating on a larger scale, according to zoom V in [Fig.3], the contact between a support and main bodies of different cathodes belonging to the battery of the preceding figures.

[0075] [Fig.6] is a front view illustrating on a larger scale, according to arrow VI in [Fig.3], the electrical energy storage module belonging to the battery of the previous figures.

[0076] [Fig.7] is a top view illustrating on a larger scale, according to arrow VII in [Fig.3], the electrical energy storage module belonging to the battery of the previous figures.

[0077] [Fig.8] is a top view, illustrating a frame involved in the manufacture of the battery of the preceding figures.

[0078] [Fig.9] is a longitudinal sectional view, illustrating some of the constituent elements of the battery, put in place at the end of a first step of a method of manufacturing the battery according to the invention.

[0079] [Fig. 10] is a longitudinal sectional view, illustrating the various constituent elements of the battery, put in place at the end of a second step of a method of manufacturing the battery according to the invention.

[0080] [Fig. 11] is a longitudinal sectional view, illustrating the various constituent elements of the battery, put in place at the end of a third step of a method of manufacturing the battery according to the invention.

[0081] [Fig. 12] is a longitudinal sectional view, illustrating the various constituent elements of the battery, put in place at the end of a fourth step of a method of manufacturing the battery according to the invention.

[0082] [Fig. 13] is a longitudinal sectional view, illustrating the various constituent elements of the battery, put in place at the end of a fifth step of a method of manufacturing the battery according to the invention.

[0083] [Fig. 14] is a schematic view, illustrating the integration of an electrical energy storage device according to the invention in an energy consuming assembly.

[0084] [Fig. 15] is a side view, similar to [Fig.2], schematically illustrating a support and an electrical energy storage module according to the prior art.

[0085] [Fig. 16] is a front view similar to [Fig. 6], illustrating an electrical energy storage module according to an alternative embodiment of the invention.

[0086] [Fig. 17] is a top view, illustrating a cutting step occurring in a first method of manufacturing the storage module of [Fig. 16].

[0087] [Fig. 18] is a top view, similar to [Fig. 17], illustrating a cutting step occurring in a second method of manufacturing the storage module of [Fig. 16].

[0088] [Fig. 19] is a side view, similar to [Fig.2], schematically illustrating another type of electrical energy storage device according to the invention.

[0089] [Fig.20] is a side view, similar to [Fig.2], schematically illustrating schematically illustrating another type of electrical energy storage device according to the invention.

[0090] [Fig.21] is a side view, similar to [Fig.2], schematically illustrating schematically illustrating another type of electrical energy storage device according to the invention.

[0091] The following reference numerals are used in the figures and in the description which follows.

[0092] 1 Battery

[0093] 11 Front (upper) face of 1

[0094] 12 Rear (lower) front face of 1

[0095] 13 to 16 Side faces of 1

[0096] 2 Stacking (storage module)

[0097] 2' Draft (not impregnated) of 2

[0098] 21, 22 Opposite front faces of 2

[0099] 23, 24 Lower (23) and upper (24) side face of 2

[0100] 25, 26 Side connection faces

[0101] 3 Anode

[0102] 31,32 Main body (31) and secondary body (32) of 3

[0103] 32 Secondary body of 3

[0104] 33 Free space between 31 and 32

[0105] 301,302; 303,304 Longitudinal edge (301,302) and transverse edge (303,304) of 3

[0106] 311, 312 Longitudinal edge of 31

[0107] 321, 322 Longitudinal edge of 32

[0108] 331, 332 Lower (331) and upper (332) ends of 33

[0109] 4 Cathode

[0110] 41, 42 Main body (41) and secondary body (42) of 4

[0111] 43 Free space between 41 and 42

[0112] 401, 402; 403, 404 Longitudinal edge (401,402) and transverse edge (403,404) of 4

[0113] 411, 412 Longitudinal edge of 41

[0114] 421, 422 B longitudinal edge of 42

[0115] 431,432 Lower (431) and upper (432) ends of 43

[0116] 5 Support

[0117] 51, 52 Front or upper face (51) and rear or lower face (52) of 5

[0118] 53, 54 Openings of 5

[0119] 55 Central sole of 5

[0120] 56, 57 Side bands of 5

[0121] 58.59 Plots of 5 (mutually isolated)

[0122] 60, 61 Anodic (60) and cathodic (61) contact members

[0123] 62 Non-conductive glue

[0124] 7 Encapsulation system

[0125] 70; 71,72 Central zone (70) and intermediate regions (71, 72) of 7

[0126] 73 Return of 7

[0127] 8 Stiffening system

[0128] 505 Frame

[0129] 507 Encapsulation material

[0130] 508 Stiffening material

[0131] 509 Ionic liquid droplets

[0132] 550 Peripheral border of 505

[0133] 551 Preforms

[0134] 555 Central range of 551

[0135] 556, 557 Side blocks of 551

[0136] 553, 554 Slots

[0137] 558, 559 Horizontal, vertical rods

[0138] 560, 561 Conductive glue

[0139] 601, 701, 901 Batteries according to three different variants of the invention

[0140] 602, 702, 902 Stacking

[0141] 603a to 603n, 703a to 703n, 903a to 903n Anodes

[0142] 604a to 604n, 704a to 704n, 904a to 904n Cathodes

[0143] 605, 705, 905 Support

[0144] 607 Encapsulation material

[0145] 608, 708 Stiffening material

[0146] 660, 760, 960 Contact member

[0147] 801 Battery according to the state of the art

[0148] 802 Storage module of 801

[0149] 803, 804 Upper electrodes of 802

[0150] 805 Connection support of 801

[0151] 860, 861 Contact organs of 801

[0152] 858, 859 Connection regions of 805

[0153] 1000 Energy consumption set

[0154] 1004 Energy consumption element

[0155] 1002 Body of 1000

[0156] 1006, 1007 Connection line

[0157] 2002 Stacking

[0158] 2003 Anode

[0159] 2004 Cathode

[0160] 2033 Free space

[0161] 2330 Crossing branch

[0162] 2301 and 2302 Longitudinal edges

[0163] 2331 Auxiliary branch

[0164] 2303 and 2304 Transverse edges

[0165] 2035 Tertiary body

[0166] 2041 Main body

[0167] 2070, 3070, 2080 Slots

[0168] 2071, 3071 Crossing channel of 2070, 3070

[0169] 2072, 3072 Auxiliary channel of 2070, 3070

[0170] E8 Smallest thickness of 8

[0171] e(60) Thickness of the contact members according to the invention

[0172] E(860) Thickness of the contact members 860 according to the state of the art

[0173] P2 Median plane of 2

[0174] G509, H509 Flow directions of 509

[0175] P5 Median plane of 5

[0176] Y2 Median transverse axis of 2 Description of the invention

[0177] Unless otherwise indicated, the term “conductor”, used as a noun or adjective, means herein: “electronic conductor”.

[0178] The term "electrode" is used here in a general sense (like the French language dictionary "Le Nouveau Petit Robert", published in June 1996) and designates a conductor through which the electric current "arrives or leaves (...) in a medium where it is to be used". In this sense, the term "electrode" includes in particular electronic and / or ionic conductors subject to electrochemical reactions; nevertheless the presence of electrochemical reactions is not required for the purposes of the invention, so that the term "electrode" as used here also designates for example the conductors in a capacitor (for which other terms may be used, depending on the type of capacitor, such as the term "plate" in the case of a plate capacitor).

[0179] The present invention relates to an electrical energy storage device, in particular of the battery, capacitor or supercapacitor type, comprising an energy storage module. It can be applied to a wide variety of types of batteries, capacitors and supercapacitors. In the following, the invention will be presented mainly in relation to electrochemical systems based on lithium ions, but it can also be implemented with electrochemical systems based on ions of sodium or potassium, for example.

[0180] We summarize here the main electrochemical systems that can be used, knowing that this list is not exhaustive.

[0181] For “Lithium technologies” (or Li-Ion technologies), there are, in addition to lithium ion battery systems (LiB, Li-Ion Batteries), lithium ion capacitors (LIC, Li-Ion Capacitors), lithium-sulfur (LiS) batteries and capacitors, and lithium-air (Li-O2) batteries and capacitors.

[0182] For "Sodium technologies" (or "Na-Ion" technologies), there are, in addition to sodium ion battery systems (SIB, Sodium-ion Batteries), sodium ion capacitors (SIC, Sodium-Ion Capacitor), sodium-sulfur type batteries and capacitors (NaS), sodium-air type batteries and capacitors (Na-O2).

[0183] For “Potassium technologies” (or “K-Ion” technologies), there are, in addition to potassium ion battery systems (PIB, Potassium-Ion Batteries), potassium ion capacitors (PIC, Potassium-Ion Capacitors).

[0184] Here we give examples for the cathode materials of SIB batteries.

[0185] Materials based on transition metal oxides can be used, and in particular:

[0186] NaxMO2+z with M chosen from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te ... and z can be equal to 0;

[0187] NaxMu / 2M'v / 2O2+zwith u + v = 2 and M, M'chosen from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te; NaxMu / 3M'v / 3M”w / 3O2+zwith u + v + w = ​​3 and M, M', M” chosen from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te.

[0188] Materials based on Prussian Blue (PB) and / or PBA (Prussian Blue Analogs) can be used, and in particular based on AxMi[M2'(CN)6]y.nH2O, in which the transition metals Mi and M2' are adjusted with the N and C atoms of the CN ligands to form an open three-dimensional network from the chains MrN = C-M2' (where = denotes a triple bond). The electrochemical performances are adjusted by the choice of the transition metals Mi and M2'. Mi and M2' can be identical. Mi can be an alloy of different transition metals. The transition metals used are taken for example from Fe, Ni, Co, Mn.

[0189] It is also possible to use materials based on polyanionic compounds, and in particular:

[0190] - compounds of the NaxM2(XO4)3 type with M = V, Ti, Fe, Cr, Mn, Co, Ni, Sc and X = P, S, As, Si, Mo or W, compounds of type NaxM3(XO4)2(X2O7) with M = V, Ti, Fe, Cr, Mn, Co, Ni, Sc and X = P, S, As, Si, Mo or W;

[0191] - compounds of type NaxM(X2O7) with M = V, Ti, Fe, Cr, Mn, Co, Ni, Sc and X = P, S, As, Si, Mo or W;

[0192] - compounds of the NaxM2(XO4)2F3 type with M = V, Ti, Fe, Cr, Mn, Co, Ni, Sc and X = P, S, As, Si, Mo or W;

[0193] - compounds of type NaxM2(XO4)2F3 yOywith M = V, Ti, Fe, Cr, Mn, Co, Ni, Sc and 0.07 < y < 0.12 and X = P, S, As, Si, Mo or W;

[0194] - compounds of type NaxM2O2(XO4)2F with M = V, Ti, Fe, Cr, Mn, Co, Ni, Sc and X = P, S, As, Si, Mo or W;

[0195] - compounds of type NaMXO4 with M = V, Ti, Fe, Cr, Mn, Co, Ni, Sc and X = P, S, As, Si, Mo or W.

[0196] Here we give examples for the anode materials of SIB and SIC type devices.

[0197] Anodes based on alloys can be used, these alloys preferably being based on Si, Ge, Sn, Sb, Bi, P, and alloys of these different compounds can be used.

[0198] Anodes based on Mxenes can be used. MXenes are a class of 2D materials with stoichiometry of the Mn+iXnTx type where M denotes a transition metal, and X is chosen from C and / or N, and T denotes a surface termination preferably chosen from F, Cl, Br, O, S, Se, Te, OH, NH2.

[0199] Conversion anodes can be used, formed in particular from the following materials:

[0200] - oxides of type Na2Ti3O7 Na4Ti5Oi2NaTi2(PO4)3;

[0201] - the oxides, sulfides, selenides, phosphide of the following elements or their alloys: Si, Ge, Sn, Sb, Bi.

[0202] For the cathodes of the PIBs, the same materials can be used as for the SIBs, but sodium is replaced by potassium.

[0203] For the PIB and PIC anodes, the same materials can be used as for the PICs, but sodium is replaced by potassium.

[0204] The geometric structure of the devices according to the invention will now be described in detail, in relation to the figures.

[0205] [Fig.l] illustrates an electrical energy storage device, in accordance with a first variant of the first main embodiment of the invention. This electrical energy storage device, which is of the electrochemical type, is a battery designated as a whole by the reference 1. This battery firstly comprises a stack 2 comprising at least one first electrode 3 and at least one second electrode 4, of polarity opposite to that of the first electrode, arranged one next to the other in an alternating manner.

[0206] In the following, the invention will be explained for the case where the first electrode 3 is an anode and the second electrode 4 is a cathode; the reverse situation is possible. The physicochemical structure of each anode or cathode, which may be of the type known, does not form part of the invention and will only be described briefly. Each anode, respectively cathode, comprises an active anode layer, respectively an active cathode layer. Each of these active layers can be solid, i.e. dense or porous in nature.

[0207] Furthermore, in order to avoid any electrical contact between two adjacent sheets, an electrolyte layer or a separator is arranged on at least one of these two sheets, in contact with the facing sheet. The electrolyte layer or the separator, not shown in the figures describing the present invention, is interposed between two sheets of opposite polarity, i.e. between the anode sheet and the cathode sheet. The aforementioned separator is then impregnated with an electrolyte, by any suitable means.

[0208] In this way, the stack 2 once produced successively comprises at least one anode sheet, at least one layer of an electrolyte material or of a separator impregnated with an electrolyte, and at least one cathode sheet. Typically this stack comprises between 10 and 100 anode and cathode sheets, arranged in an alternating manner as described above.

[0209] As shown in particular in [Fig.6] each anode 3 comprises a main body 31, also called primary body, as well as a secondary body 32. These respectively main and secondary bodies are separated by a so-called free space 33, which is free of any electrode material, as well as of any current collector substrate. By convention the free space 33 extends transversely, connecting the so-called longitudinal edges 301 and 302 of the anode. Each longitudinal edge 301, 302 is formed by a longitudinal edge 311, 321 of the main body, as well as a longitudinal edge 312, 322 of the secondary body. Finally, 303 and 304 denote the so-called transverse edges of the anode 3, corresponding to the edges of the bodies 31 and 32 opposite each free space.

[0210] Similarly, each cathode 4 comprises a main body 41 and a secondary body 42, separated by a so-called free space 43, connecting the longitudinal edges 401 and 402 of the cathode. Each longitudinal edge 401, 402 is formed by a longitudinal edge 411, 421 of the main body, as well as a longitudinal edge 412, 422 of the secondary body. Finally, 403 and 404 denote the so-called transverse edges of the cathode 4, which form the transverse edges of the main 41 and secondary 42 bodies respectively, edges which are opposite the free space. In [Fig.6], the transverse edges 303 and 403 are merged, as are the transverse edges 304 and 404.

[0211] Advantageously, as illustrated in [Fig. 6], both the free spaces 33 of the different anodes and the free spaces 43 of the different cathodes are superimposed. Furthermore, the two series of free spaces 33 and 43 are mutually symmetrical, with respect to a median transverse axis Y2 (see [Fig. 6]) of the stack 2. In [Fig. 6], the opposite longitudinal ends of the aforementioned free spaces 33 and 43 have been referenced. The ends 331 and 431 are said to be lower, with reference to a positioning normal of the battery. More precisely, these ends 331 and 431 open onto the support 5, belonging to the battery according to the invention. Furthermore, the opposite ends 332 and 432, which are called upper, are more particularly visible in [Fig.7].

[0212] Stack 2 above is for example in accordance with the teaching of WO 2020 / 136 313, or WO 2021 / 234 585, both in the name of the applicant. Similarly, this stack can be produced by a manufacturing method as described in these two documents, by making slots of any suitable shape in a superposition of alternating layers intended to form a plurality of anodes and cathodes. I-shaped slots, as disclosed in WO 2021 / 234 585, are well suited, it being understood that these slots can also have an H shape as disclosed in WO 2020 / 136 313. As will be seen in the following, in particular with reference to [Fig. 16], other alternative shapes can also be envisaged.

[0213] This stack 2, of a generally parallelepiped type, has six faces. We call, in particular with reference to [Fig. 3], P2 the so-called median plane of the main stack 2, which contains the sheet of the stack placed in the median position, which is not shown in this [Fig. 3]. This median plane extends parallel to all the sheets respectively of anode and cathode, forming this stack.

[0214] In [Fig.2] we note 21 and 22 the opposite front faces of the stack which, by convention, are substantially parallel to the different electrodes 3 and 4 above. The stack 2 also defines four lateral faces 23 to 26, which are two by two mutually parallel and opposite. 23 designates the lateral face, called lower or contact face. Indeed, as we will see below, this face is positioned in normal service in the lower position, while allowing electrical contact with a support described later. 24 designates the lateral face, called upper or opposite to that 23, while 25 and 26 (see [Fig.l]) designate the lateral faces called connection faces in that they connect 23 and 24.

[0215] The battery 1 according to the invention further comprises a support, designated overall by the reference 5. This support 5, which is generally flat, typically has a thickness of less than 300 μm, preferably less than 100 μm. In a manner similar to what was explained above for the stack 2, P5 denotes the so-called median plane of the support 5 (see [Fig. 3]). This support is advantageously made of an electrically conductive material, typically a metallic material, in particular aluminum, nickel, copper, stainless steel which can be coated in order to improve their solderability property with a thin layer of gold, nickel and / or tin. 51 denotes respectively the so-called "front" or "upper" front face of the support, which is facing stack 2, as well as 52 the opposite front face called “rear” or “lower” (see in particular [Fig.l]).

[0216] This support 5 comprises openings 53 and 54 (see [Fig.l]) delimiting a central sole 55 as well as two opposite lateral strips 56 and 57. The different regions 55, 56 and 57 of this support are, consequently, mutually electrically insulated. In particular, the lateral strips 56 and 57 comprise mutually electrically insulated pads 58, 59 which, as detailed below, are capable of collecting the current from the battery. In the example illustrated, the electrical insulation is achieved by providing the aforementioned openings 53 and 54 which, as will be seen in the following, are filled with a stiffening material. As a variant, it can be provided that these openings are filled with a non-conductive material, for example polymers, ceramics, glasses.

[0217] According to an essential characteristic of the invention, the geometric positioning of the stack 2 is chosen specifically. As shown in particular in Figures 2 and 3, the median main plane P2 of this stack extends substantially perpendicularly, relative to the plane P5 of the support 5. In other words, if it is assumed that the support is horizontal, the stack 2 is consequently placed vertically. In particular, this stack rests on the support 5 via its lateral face 23, which rests on the upper front face 51 of the support.

[0218] As shown more particularly in Figures 2 to 5, it is assumed that the stack 2 is formed of n anodes 3a to 3n, as well as n cathodes 4a to 4n. As variants not shown, it can be provided that this stack is formed either of n+1 anodes and n cathodes, or of n anodes and n+1 cathodes. [Fig.2] schematically illustrates the whole of this stack, mounted on the support 5, without showing the encapsulation system 7. On the other hand, the perspective of [Fig.3] represents only the first three anodes including those 3a and 3b, the last three anodes including those 3n-1 and 3n, the first three cathodes including those 4a and 4b, as well as the last three cathodes including those 4n-1 and 4n. Furthermore, on this same [Fig.3], support 5 is illustrated schematically and partially.

[0219] This stack 2 is electrically connected to the support by means of cords 60 and 61, forming respectively anodic and cathodic contact members. These cords, partially illustrated in [Fig.3], are made of a suitable conductive material, advantageously ensuring an additional mechanical fixing function. For this purpose, these cords are made in particular of a conductive glue such as, for example, a graphite glue, a glue loaded with metallic nanoparticles (Au, Cu, Al, etc.). The metallic fillers may be different for the anode and the cathode (typically Al for the cathode, Cu for the anode).

[0220] Figures 4 and 5, which correspond to much larger scale views of the details IV and V of [Fig.3], illustrate the cooperation of the stack 2 with the first 60 and second 61 cords. 3a, 3b and 3c denote the first three anodes of the stack, which are separated two by two by the first three cathodes 4a, 4b and 4c.

[0221] For each of these anodes, only the main body 31a, 31b and 31c is in contact with the cord 60. More precisely, as shown in particular in [Fig.4], each main body rests on the cord 60 via its respective longitudinal edge 311a, 311b and 311c. This allows the collection of the electrical energy produced, from these main anode bodies towards this anode cord 60. Furthermore, as shown in particular in [Fig.5], the secondary anode bodies 32a, 32b and 32c rest on the other cord 61, or cathode cord. Advantageously, the main bodies 31a to 31c are not in contact with this cathode cord 61.This helps, in particular, to prevent the occurrence of short circuits.

[0222] Similarly, only the main bodies 41a, 41b and 41c of the cathodes are in contact with the cathode cord 61, via their respective longitudinal edges 411a, 411b and 411c (see more particularly [Fig.5]). This allows the collection of the electrical energy produced, from these main cathode bodies towards this cathode cord 61. Furthermore, as shown in particular in [Fig.4], the secondary cathode bodies 42a, 42b and 42c rest on the anode cord 60. Similarly to what was described in the previous paragraph, the main cathode bodies 41a to 41c are advantageously not in contact with this anode cord 60, in order in particular to avoid short circuits.

[0223] As a variant not shown, a layer of non-conductive glue may be provided, represented by the dotted arrow 62 (see in particular [Fig.l]). This layer, typically formed by means of a non-conductive glue, in particular of the epoxy or acrylate type, makes it possible to consolidate the fixing between the support and the stack. As a variant, it may be provided to replace this non-conductive glue by means of a weld, also not shown. The thickness of this layer 62 is typically between 5 and 100 pm, in particular close to 50 pm. According to the main plane of the support 5, this layer at least partially covers the openings 53 and 54 above, so as to mutually isolate the anodic and cathodic contact members.

[0224] As a variant not shown, it is also possible to provide for these cords 60 and 61 to be made of a material other than a conductive adhesive. For example, mention will be made of ultrasonic welding or the like, or any other suitable means capable of providing a conductive function as well as, where appropriate, a mechanical fixing function. It will be noted that the welding can provide a mechanical function, in addition to its conductive function. If a means makes it possible to provide a conductive function but not a mechanical function, the mechanical fixing between the stack and the support is then provided by the layer of glue 62 which, in this case, is not optional.

[0225] The battery according to the invention may further comprise an encapsulation system, designated as a whole by the reference 7 (see in particular [Fig.l]). This encapsulation system 7 firstly comprises a central zone 70, covering the lateral face 24 of the stack. This central zone is extended, on either side, by intermediate regions, or wings 71 and 72, covering the front faces 25 and 26 of the stack. Finally, these wings are themselves extended by a return 73 covering a part of the front face 51 of the support 5.

[0226] This encapsulation system 7 can be made of any material, making it possible to ensure a sealing function. For the purposes of the invention, this function is ensured by any encapsulation system which preferably has a water vapor permeance (WVTR coefficient or “WVTR”) of less than 105 g / m2.d. The measurement of the water vapor permeance can be carried out using a method which is the subject of US 7,624,621 and which is also described in the publication “Structural properties of ultraviolet cured polysilazane gas barrier properties on polymer substrates” by A. Morlier et al., published in the journal Thin Solid Films 550 (2014) 85-89. The lower the WVTR coefficient, the more the encapsulation system is sealed.

[0227] Said encapsulation system advantageously comprises one or more layers which have been deposited from a vapor phase, and preferably by a technique selected from the group formed by: atomic layer deposition (ALD), plasma-enhanced chemical vapor deposition (PECVD), high-density plasma chemical vapor deposition (HDPCVD).

[0228] For example, we will choose to deposit: - a dense inorganic film deposited by ALD, PECVD or HDPCVD with a thickness of less than 5 pm and preferably less than 2 pm. The inorganic film may in particular be made of SiO2, Si3N4, SiC, Ta2O5, amorphous Si or Al2 O3; - a succession of inorganic films with a total thickness of less than 5 μm and preferably less than 2 μm. These inorganic films may in particular be made of SiO2, Si3N4, SiC, Ta2O5, amorphous Si or A12O3 and may be deposited, taking into account their chemical nature, using any suitable technique, dry or wet (such as: PECVD, PVD, ALD, Spray coating + UV conversion, Sol - gel, etc.); - a succession of organic and inorganic films with an individual thickness of less than 20 pm and preferably less than 10 pm. The inorganic films may be made of SiO2, Si3N4, SiC, amorphous Si, and may be deposited, taking into account their chemical nature, using any appropriate dry or wet technique (such as: PECVD, PVD, ALD, Spray coating + UV conversion, Sol-gel). Organic films can be polymer films (in particular polyvinylidene fluoride (abbreviated PVDF), parylene, acrylate).

[0229] Finally, the battery according to the invention as shown in [Fig. 1] is equipped with a stiffening system, designated as a whole by the reference 8. This stiffening system covers the entire encapsulation system 7, opposite the support 5. It also covers at least part and, advantageously as in the example illustrated, the entire front face of the support 5.

[0230] In order to guarantee the advantageous criterion of sealing, it is necessary to ensure that the components, potentially harmful to the proper functioning of the battery, cannot access the elementary stack of anodes and cathodes. In other words, in accordance with the invention, it is a question of avoiding any potential entry point for these harmful components. To this end, the encapsulation material 7 also advantageously occupies the openings 53, 54 of the support 5. It will be noted that the stiffening material 8 also advantageously fills these openings, by being intimately linked to the encapsulation material. In [Fig.l], the references 7 and 8, as well as 53 and 54, have been given in the same areas corresponding to these openings, in order to visualize their filling by these various materials.

[0231] This stiffening system 8 can be made of any material, making it possible to ensure this mechanical rigidity function. With this in mind, for example, a resin will be chosen which may consist of a simple polymer or a polymer loaded with inorganic fillers. The polymer matrix may be from the family of epoxy, acrylates, fluorinated polymers for example, the fillers may consist of particles, flakes or glass fibers. Advantageously, this stiffening system 8 can provide an additional function of barrier against humidity. With this in mind, for example, a glass with a low melting point will be chosen, thus ensuring mechanical resistance and an additional barrier against humidity. This glass may be, for example, selected from the group formed by the following systems: SiO2-B2O3, Bi2O3-B2O3, ZnO-Bi2O3-B2O3, TeO2-V2O5, PbO-SiO2.

[0232] As seen above, the thickness of the encapsulation system 7 is advantageously very small, in particular less than 20 μm, preferably less than 10 μm. Typically, the stiffening system 8 has a thickness much greater than that of the encapsulation system 7. With reference to [Fig. 1], E8 denotes the smallest thickness of this stiffening system, at the level of the covering of the front face of the stack. Advantageously, this thickness E8 is between approximately 20 μm and approximately 250 μm, typically between approximately 40 μm and approximately 200 μm, for example around 100 pm.

[0233] The battery 1 according to the invention, as shown in [Fig.l], generally has the shape of a parallelepiped. 11 denotes its front or upper frontal face, 12 its rear or lower frontal face, as well as 13 to 16 its various lateral faces. Given the specific positioning of the stack 2 described above, the upper frontal face 11 of the battery 1 corresponds to the lateral face 24 of the stack. Furthermore, the lateral faces 13 and 14 of this battery 1 correspond to the opposite frontal faces 21 and 22 of the stack, while the other lateral faces 15 and 16 of the battery correspond to the other lateral faces 25 and 26 of the stack. By way of non-limiting examples, the thickness El (see [Fig.l]) of the battery is for example between approximately 0.5 mm and approximately 2.5 mm, while its transverse dimensions L1 (see [Fig.2]) and 11 (see [Fig.l]) are for example between approximately 1 mm and approximately 4 mm.

[0234] In operation, in a conventional manner, electrical energy is produced by an electrochemical conversion at the level of the elementary stack. This energy is transmitted to the conductive pads 58 and 59 of the support 50, via the glue beads 60 and 61. Since these pads are mutually insulated, any risk of short circuit is avoided. It will be noted that the electrical energy is transmitted from the main bodies 31 and 41, belonging to both the anodes and the cathodes. This is advantageous in terms of efficiency, since these main bodies form the major part of the surface of the anodes and the cathodes. Furthermore, this transmission is carried out via the longitudinal edges of these main bodies, which contributes to further improving the efficiency compared to a transmission via the transverse edges.

[0235] This electrical energy is then directed, from the conductive pads 58 and 59, to an energy consumption assembly of any suitable type. In [Fig. 14], this energy consumption device is shown schematically, being assigned the reference 1000. It comprises a body 1002, on which the lower face of the support rests. The mutual fixing between this body 1002 and the support 5 is carried out by any suitable means.

[0236] Said assembly 1000 further comprises an energy consuming element 1004, as well as connection lines 1006 1007 electrically connecting the regions 56 57 of the support 5 with this element 1004. The control can be ensured by a component of the battery itself, and / or by a component not shown belonging to the assembly 1000. This component, which is of any suitable type, is for example an LDO type component (which means in English “Low Dropout Regulator”, namely a regulator with a low voltage drop).

[0237] As non-limiting examples, such an energy consumption set may be an amplifier type electronic circuit, a clock type electronic circuit (such as an RTC component, Real Time Clock), a volatile memory type electronic circuit, a static random access memory (SRAM, Static Random Access Memory) type electronic circuit, a microprocessor type electronic circuit, a watchdog timer type electronic circuit, a liquid crystal display type component, an LED (Light Emitting Diode) type component, a voltage regulator type electronic circuit (such as a low-dropout voltage regulator circuit, abbreviated LDO, Low-dropout regulator), a CPU (Central Processing Unit) type electronic component.

[0238] As a variant not shown, it is possible to provide that the electrochemical device according to the invention comprises several additional electronic components. Typically, it is possible to envisage producing a mini circuit providing a complex electronic function. In this spirit, it is possible to use an RTC module (which means in English "Real Time Clock", namely a clock function), or an energy recovery module (in English "Energy Harvesting"). It is also possible to provide an electronic component capable of controlling the battery of [Fig. 18] above, which is integrated into an energy consuming device.

[0239] We will now describe, with reference to Figures 8 to 13, different steps of a method for manufacturing the battery 1 described above. In order to implement this method, a frame 505 is advantageously used, which is intended to form a plurality of supports 5. This frame 505, which is shown on a large scale in [Fig.8], is similar to that described in particular in [Fig.2] of WO 2021 / 130 688. It has a peripheral edge 550, as well as a plurality of preforms 551, each of which allows the manufacture of a respective battery. In the illustrated example, there are twelve mutually identical preforms, distributed along three rows and four columns. As a variant, it is possible to use a frame having a different number of such preforms.

[0240] Each preform comprises a central area 555, intended to form the sole 55, as well as two lateral blocks 556 and 557 intended to form the strips 56 and 57 respectively. The area and the blocks are mutually separated by slots 553 and 554, which are intended to form the openings 53 and 54. The different preforms are immobilized, both relative to each other, as well as relative to the peripheral edge, by means of different rods, respectively horizontal 558 and vertical 559.

[0241] In a first step, which is illustrated in [Fig.9], a respective dose 560, 561 of conductive glue is deposited on each lateral block 556 and 557, intended to form the cords 60, 61. In a manner not shown, an additional dose of non-conductive glue can also be deposited on each area 555, intended to form the optional layer 62.

[0242] In a second step illustrated in [Fig. 10], different blanks 2' are placed on the doses of conductive glue 560 and 561, the structure of which is similar to that of the final stacks 2. According to a particularly advantageous characteristic of the invention, these blanks 2' differ from the stacks 2, only in that they are not impregnated with electrolyte.

[0243] These blanks are arranged, relative to the areas 555 and the blocks 556, 557, in the precise position that the final stacks must adopt with respect to the sole 55 and the lateral strips 56, 57. At the end of this step, the lower ends 331 and 431 of the free spaces open out opposite the upper face 595 of the central area 555. Advantageously, as will be explained below, the opposite ends 332 and 432 are said to be open, namely that they are easily accessible.

[0244] In a third step, which is illustrated in [Fig.l 1], the different blanks 2' above are impregnated with a liquid electrolyte which is advantageously an ionic liquid. To do this, a nozzle (not shown in the figures) of a type known per se is typically used. This nozzle is adapted to deliver droplets 509 of ionic liquid whose size, typically nanoscopic, allows this impregnation. The ionic liquid, forming an electrolyte, is supplied at the level of the lateral face 24' of the blank 2'. In this way, the impregnation towards the mesopores, which is typically carried out by capillarity, is facilitated under the effect of gravity. This ionic liquid penetrates inside the blank, on the one hand via the upper ends 332 and 432 of the free spaces according to the arrows G509, on the other hand directly via the pores of the electrodes according to the arrows H509.At the end of this impregnation operation of each 2' blank, the final storage modules 2 are obtained.

[0245] In a fourth step, illustrated in [Fig. 12], a material 507 is deposited to form each encapsulation system 7. Then, in the fifth step illustrated in [Fig. 13], a material 508 is deposited to form each stiffening system 8. These materials 507 and 508 are deposited, successively, on the impregnated stacks 2. Finally, a cutout of the frame 505 is made, on which the various constituents of the plurality of batteries have been arranged. This cutout, not shown in the attached figures, is similar to that described in particular in [Fig. 8] of WO 2021 / 130 688.

[0246] We will now explain the advantages of the invention, with respect to the prior art embodied in particular by the battery in accordance with WO 2021 / 130 688. The latter 801 is illustrated schematically in [Fig. 15], which is analogous to [Fig. 2] representing the battery 1 according to the invention. In [Fig. 15], we note 805 the connection support, 858 and 859 the connection regions of the latter, 802 the module of storage as well as 860 and 861 the electrical contact organs.

[0247] Given the specific positioning of the storage module 2 according to the invention, the current coming from the different electrodes 3a, 4a, ..., 3n and 4n can be collected very satisfactorily regardless of the size of this module. Indeed, given that this current collection is ensured at the level of the lateral contact face 23, via each cord 60, 61, it is independent of the number of electrodes. On the contrary, in the prior art, when the storage module 802 has a large number of electrodes, this tends to increase the overall contact resistance due to the high thickness of the contact members 860, 861, which have an electrical resistance greater than that of the current collection pads. Consequently, the current coming from the upper electrodes 803n, 804n is collected significantly less efficiently than that coming from the electrodes close to the support.The architecture in accordance with the invention makes it possible to avoid any reduction in efficiency inherent in this state of the art.

[0248] Furthermore, the electrical contact, produced in accordance with the invention, is of the planar type. In other words, the contact members 60 and 61 are formed by a so-called “contact” adhesive as opposed to the volume adhesive of the prior contact members 860 and 861. In this spirit, the thickness e(60) of the contact members according to the invention is as small as possible so as to reduce the resistance, advantageously being less than 100 μm (microns). On the other hand, in the prior art, the thickness E(860) of the contact members corresponds substantially to the total thickness of the storage module. This total thickness, which depends on the space constraints of the device, is in any case very significantly greater than the thickness e(60) mentioned above. The planar type contact, in accordance with the invention, is mechanically more reliable and less resistive.

[0249] Furthermore, according to the particularly advantageous characteristic of the invention illustrated in particular in [Fig. 11], the impregnation can be carried out after the mounting of the storage module 2 on its support 5. Under these conditions, during mounting, the module 2 is significantly less sensitive to high temperature heat treatments than the module 802 of the prior art. Consequently, it is possible to use conductive glasses and / or ceramics, or even solder, to produce the ohmic junction between the module and the support.

[0250] It should also be noted that the presence of an encapsulation system provides specific advantages. Indeed, this encapsulation system makes it possible to produce batteries with higher capacity.

[0251] [Fig. 16] illustrates an alternative embodiment of an energy storage module, belonging to the battery according to the invention. In this [Fig. 16] the mechanical elements, similar to those of the previous figures, are assigned the same reference numbers increased by the number 2000.

[0252] The stack 2002 of this [Fig. 16], forming an energy storage module, differs from that 2 in particular in that each anode 2003 has a structure different from that of each anode 3, while each cathode 2004 has a structure identical to that of each cathode 4. However, as an alternative not shown, it can be provided that each cathode 2004 has a structure different from that 4, while each anode 2003 is identical to that 3.

[0253] With reference to [Fig. 16], the free space 2033 of each anode 2003 firstly comprises a so-called through branch 2330, similar to the free space 33 above, which connects the longitudinal edges 2301 and 2302 of this anode. In accordance with the present variant, the free space 2033 further comprises a so-called auxiliary branch 2331, which connects the through branch 2330 with the opposite transverse edge 2304 of the anode 2003. Consequently, the auxiliary branch separates the main body 2031 from a so-called tertiary body 2035. Furthermore, the through branch separates the secondary body 2032 from both the main body 2031 and the tertiary body 2035 above.

[0254] The positioning and fixing of the storage module 2002 above are similar to those described previously, with reference to the storage module 2. In service, the energy is transmitted from the longitudinal edges of the main body 2031 explained above, as well as from the main body 2041 which we have seen is identical to that 4L. In order to guarantee maximum efficiency, the surface area of ​​the tertiary body is as small as possible, while guaranteeing its mechanical strength.

[0255] The embodiment variant of [Fig. 16] has specific advantages. Indeed, it makes it possible to avoid short-circuit problems at the upper and lower faces of the storage module, namely the longitudinal edges of the latter. Such short circuits are likely to be induced during the cutting steps involved in the manufacturing process of the blanks 2' or the storage module 2.

[0256] This variant of [Fig. 16] defines another object of the invention, namely an energy storage module (2002) comprising

[0257] - at least one first electrode (2003) and at least one second electrode (2004), which are arranged one above the other in an alternating manner,

[0258] - at least one electronic separator, each separator separating a first electrode and a second adjacent electrode,

[0259] both the first electrode and the second electrode each comprising a main body (2031; 2041), a secondary body (2032; 2042) and a so-called free space (2033; 2043), which is free of any electrode material and / or any current collector substrate, each free space separating a respective main body and a secondary body,

[0260] module in which the free space (2033) of each first electrode, or of each second electrode, comprises a through branch (2330) connecting the longitudinal edges of said electrode as well as an auxiliary branch (2331) connecting the through branch with the transverse edge (2304) opposite said electrode, the auxiliary branch separating the main body (2031) from a so-called tertiary body (2035) while the through branch separates the secondary body (2032) from both the main body and the tertiary body.

[0261] Examples of manufacturing the module 2002, described above, are briefly given with reference to Figures 17 and 18. The present [Fig. 17] partly repeats [Fig. 6] of WO 2021 / 234 585 discussed above, which has as its object the production of I-shaped slots in a superposition of alternating strata. In the present [Fig. 17] each slot 2080 illustrated in dotted lines, arranged in each stratum intended to form a respective cathode 2004, has an I-shape as in WO 2021 / 234 585.

[0262] On the other hand, each slot 2070, arranged in each layer intended to form a respective anode 2003, has a through channel 2071, as well as an auxiliary channel 2072. These channels are intended to form, respectively, the through branch 2330 as well as the auxiliary branch 2331 of each anode 2003 of [Fig. 16]. The cutouts made in the different layers, shown by the different dot-and-dash lines of [Fig. 17], are similar to those described in WO 2021 / 234 585, so they will not be described in more detail.

[0263] The present [Fig. 18] partly repeats [Fig. 5] of WO 2020 / 136 313 discussed above, which has as its object the production of H-shaped slots in a superposition of alternating layers. Each slot formed in each layer intended to form a respective cathode 2004, has an H shape as in WO 2020 / 136 313. In the present [Fig. 18], only the horizontal connecting channel 3080 of each cathode slot is visible.

[0264] On the other hand, each slot 3070, arranged in each layer intended to form a respective anode 2003, has an additional auxiliary channel 3072, extending from the horizontal connecting channel 3071. These channels are intended to form, respectively, the auxiliary branch 2331 and the through branch 2330 of each anode 2003 of [Fig. 16]. The cutouts made in the different layers, shown by the different dot-and-dash lines of [Fig. 18], are similar to those described in WO 2020 / 136 313, so they will not be described in more detail.

[0265] The invention is not limited to the examples described and shown.

[0266] It can first be provided that the connection support is devoid of a central sole, as described in [Fig. 15] of WO 2021 / 130 688.

[0267] Furthermore, it can be provided that the energy storage device, in accordance with the invention, incorporates an additional electronic component. This method of rea lisation is to be compared to that described in figures 16 and 17 of WO 2021 / 130 688. This energy storage device can be equipped with several additional electronic components, according to the variant mentioned in WO 2021 / 130 688 without however being illustrated therein.

[0268] As an additional variant not shown, it may be provided that the energy storage device according to the invention is devoid of a stiffening system, such as that 8. This variant finds its application in particular in the case where the encapsulation system 7 has high mechanical resistance.

[0269] In the embodiment described and shown, the conductive support 5 is of the single-layer type. As a variant, this support may on the contrary be multi-layer, for example having one of the geometries described in FIGS. 25 to 29 of WO 2021 / 130 688.

[0270] As an additional, particularly advantageous variant, it is possible to place, on the same support, several batteries connected either in series or in parallel. These batteries are then arranged under a common encapsulation system. It is already known to associate batteries in parallel, but according to the state of the art, the total thickness of the batteries is limited industrially by the possibility of cutting. According to the invention, the capacity of the battery can be increased by cutting two batteries of thinner thicknesses and connecting them together in the same encapsulation system. This is less expensive than producing two separate encapsulation systems.

[0271] Similarly, some electronic circuits require higher operating voltages than the voltages delivered by an elementary cell. According to the invention, two or more batteries can be connected in series under the same encapsulation system.

[0272] According to another embodiment, it is possible to combine, under the same encapsulation system, a microbattery with a supercapacitor and / or a capacitor connected in parallel. Preferably, in such a combination, the operating voltage of the capacitor and / or supercapacitor is higher than the maximum voltage of the battery. The two components being connected in parallel, the microbattery then charges the capacitor which can, when the current demand is at a maximum, assist the battery in supplying current. This microbattery is preferably rechargeable.

[0273] According to another embodiment, the components mounted in parallel can be two microbatteries of different chemistry, with different voltages; these microbatteries can both be rechargeable, but it is also possible to associate a primary battery with a secondary battery, for example a high-capacity primary battery with a small high-power secondary battery.

[0274] Typically, the microbatteries according to the invention are designed to be compatible with microelectronics manufacturing processes.

[0275] Typically, the batteries according to the invention can be produced: - either with “all-solid” type layers, i.e. without impregnated liquid or pasty phases (said liquid or pasty phases can be a conductive medium for lithium, sodium or potassium ions, capable of acting as an electrolyte), - either with mesoporous “all-solid” type layers, impregnated with a liquid or pasty phase, typically a conductive medium of lithium, sodium or potassium ions, which spontaneously enters the layer and no longer comes out of this layer, so that this layer can be considered as quasi-solid, - either with impregnated porous layers (i.e. layers presenting a network of open pores which can be impregnated with a liquid or pasty phase, and which gives these layers wet properties).

[0276] In the above, reference has been made more particularly to an electrochemical type electrical energy storage device, in the form of a battery. This battery, which has been described as being lithium ion battery, may also be sodium ion battery, but also potassium ion battery. The invention also finds application to other electrical energy storage devices (which are not necessarily all electrochemical type), in particular certain types of capacitors or supercapacitors.

[0277] In particular, the invention can be applied to different types of supercapacitors. It can be applied to electrochemical double layer supercapacitors, which operate by adsorption of capacitive charges at the interface of an electrolyte and a polarizable electrode with a large specific surface area; the surface charges are located in the electrochemical double layer, adsorbed on the surface of the electrode.

[0278] The invention can also be applied to pseudo-capacitors, which implement rapid and reversible faradaic reactions at the surface of the electrodes (these reactions are also called "surface conversion reactions"). Pseudo-capacitive materials are typically conductive polymers, or certain metal oxides (RuO2, MnO2), or certain transition metal nitrides. The capacity of these materials is very high, but they generally operate with electrolytes not containing insertion ions or in an aqueous medium, which limits the operating voltage of the cell.

[0279] The invention can also be applied to hybrid supercapacitors. The term "hybrid" refers to the fact that the nature of the reactions at the cathode and anode is not not the same: at the cathode these are surface reactions (adsorption or conversion), while at the anode these are reactions of insertion of ions in volume. Among the hybrid supercapacitors we mention here the lithium ion supercapacitor (LIC - Lithium Ion Capacitor), or sodium ion supercapacitor (NaC - Sodium Ion Capacitor), or potassium ion supercapacitor (KC - Potassium Ion Capacitor), which is a hybrid structure implementing a dual structure composed of two electrodes of different types: an electrode with insertion of lithium, respectively sodium or potassium, as anode, and a cathode with a high specific surface. The anode is preferably very conductive of ions and electrons, has a large specific surface and is capable of inserting cations. This insertion of cations in the anode is not limited to the surface, it proceeds in the entire volume of the anode.The cathode also has a large specific surface area, capable of adsorbing the counterion of the cation (i.e. the anion) contained in the electrolyte. The cathode can be made of activated carbon. Thus, the physicochemical mechanisms are different at the anode and the cathode, which is why we speak of a hybrid structure. Pseudo-capacitors generally operate in aqueous solvents, or in electrolytes not containing insertion ions.

[0280] The invention can also be applied to Metal-Insulator-Metal type capacitors (commonly abbreviated MIM) and to multilayer ceramic capacitors (commonly abbreviated MLCC).

[0281] Several types of electrolytes can be used in the supercapacitors according to the invention. Aqueous electrolytes can be used in pseudocapacitors and EDLC type supercapacitors. The use of aqueous electrolytes limits the range of potential use, but has the advantage of not requiring an encapsulation system having total water vapor tightness. In order to increase the operating voltage range and the energy density of the supercapacitors, and in particular hybrid supercapacitors with lithium ions, sodium ions or potassium ions, electrolytes based on organic solvents and / or ionic liquids can be used; these electrolytes are then sensitive to humidity, and the supercapacitors must have an encapsulation system.

[0282] In [Fig. 19] a first type of supercapacitor 601 is illustrated, which may in particular be a hybrid supercapacitor such as a lithium ion hybrid supercapacitor LiC, a sodium ion hybrid supercapacitor SIHC or a potassium ion hybrid supercapacitor PIHC, or even such as an electrochemical double layer supercapacitor. In this [Fig. 19] the mechanical elements similar to those of FIGS. 1 to 18 are assigned the same reference numbers, increased by the number 600.

[0283] With regard to what has been described above, this first type differs from a battery 1 as described in the preceding figures, by the fact that the free space, provided in each electrode, is free of any electrode material and / or any current collector substrate. Apart from this difference, the capacitor or the supercapacitor according to [Fig. 19] has the same structure, in particular geometric, as that of a battery such as that 1 described previously.

[0284] We thus find an encapsulation system 607, similar to that 7 of the battery above. In this [Fig. 19] we have more particularly illustrated the storage module 602 of this supercapacitor, formed by the succession of electrodes 603a to 603n, as well as 604a to 604n. The positioning and fixing of this energy storage module of this capacitor or, relative to its electrical connection support 605, are similar to those described above with reference to the battery 1. Finally, the supercapacitor 601 has, optionally, a stiffening system 608 similar to that 8 of the battery 1 of the first embodiment. In [Fig. 19], this optional character is materialized by the fact that this stiffening system is illustrated in dotted lines.

[0285] In [Fig.20] a second type 701 of supercapacitors is illustrated, which can be a pseudo capacitor, or an electrochemical double-layer supercapacitor with an electrolyte chosen not to be sensitive to humidity. In this [Fig.20] the mechanical elements similar to those of figures 1 to 18 are assigned the same reference numbers, increased by the number 700.

[0286] Just as for the supercapacitor 601 of [Fig. 19], the free space provided in each electrode of this second type 701 is free of any electrode material and / or any current collector substrate. Furthermore, the supercapacitor 701 of [Fig. 20] differs, both from the battery 1 and from the supercapacitor 601, in that it is devoid of an encapsulation system, such as that 7 or 607 above. Indeed, the storage module 702 of this supercapacitor does not have the same sensitivity to humidity.

[0287] Consequently, this stack is associated with a simple mechanical protection system 708, typically overmolded. This mechanical protection system 708 is made of a material different from that constituting the encapsulation system 7, described previously. By way of example, this protection system 708 can be formed in a material similar to those described above, which can constitute the stiffening system 8.

[0288] In this [Fig.20] the storage module 702 of this second type of supercapacitor is more particularly illustrated, formed by the succession of electrodes 703a to 703n, as well as 704a to 704n. The positioning and fixing of this energy storage module 702, relative to its electrical connection support 705, are similar to those described above with reference to the battery 1.

[0289] In [Fig.21] a third type 901 of capacitor is illustrated, which is for example a MIM capacitor (Metal Insulator Metal) or an MLCC capacitor (multilayer ceramic capacitor). In this [Fig.21] the mechanical elements similar to those of figures 1 to 18 are assigned the same reference numbers, increased by the number 900.

[0290] The free space provided in each electrode, as defined at the beginning of the present description, belonging to this capacitor 901 is free of any electrode material, i.e. of any electronically conductive material taking into account the definition given above of the term “electrode”. Furthermore, this capacitor may be devoid of both an encapsulation system and a mechanical protection system. Consequently, no additional layer covering the storage module 902, formed by the succession of electrodes 903a to 903n, as well as 904a to 904n, is therefore provided. Although this possibility is part of the invention, it is less preferred.

[0291] Just as for the supercapacitors 601 and 701, the positioning and fixing of this energy storage module, relative to its electrical connection support 905, are similar to those described above with reference to the battery 1. It should be noted that it is advantageous to protect a MIM type capacitor against mechanical damage; this protection can be provided at the component level by a mechanical protection system, and / or by appropriate protection means at the level of the electronic card on which this component will be mounted, or at the level of the housing in which said electronic card will be integrated.

Claims

Claims

1. Electrical energy storage device, in particular of the battery (1), capacitor or supercapacitor type, comprising - an energy storage module (2) comprising - at least one first electrode (3a - 3n) and at least one second electrode (4a - 4n), which are arranged one above the other in an alternating manner, - at least one electronic separator, each separator separating a first electrode and an adjacent second electrode, both the first electrode and the second electrode each comprising a main body (31; 41), a secondary body (32; 42) and a so-called free space (33; 43), which is free at least of any electrode material and / or any current collector substrate, each free space separating a respective main body and a secondary body - this storage module comprising so-called opposite front faces (21, 22), which are parallel to the planes of the different electrodes, as well as so-called lateral faces (23 - 26), which are in particular opposed two by two, - an electrical connection support (5), made at least partly of a conductive material, comprising a first electrical connection region (58) and a second electrical connection region (59) which are electrically insulated from each other, - a first electrical contact member (60), capable of ensuring the electrical connection between each first electrode (3) and the first electrical connection region (58), - a second electrical contact member (61), capable of ensuring the electrical connection between each second electrode (4) and the second electrical connection region (59), said electrical energy storage device being characterized in that - the electrical energy storage module (2) rests, by one of its lateral faces, called the lateral contact face (23), on a front face (51) called the reception face, of the electrical connection support, - the different first electrodes being in contact, by one of their longitudinal edges, with the first contact member (60), - the different second electrodes being in contact, by one of their longitudinal edges, with the second contact member (61).

2. Electrical energy storage device according to the preceding claim, in which the different main bodies (31) of the first electrodes (3) are in contact with the first contact member (60), while the different main bodies (41) of the second electrodes are in contact with the second contact member (61).

3. Electrical energy storage device according to one of the preceding claims, in which the main plane (P5) of the support (5) and the main median plane (P2) of the storage module (2) are mutually oblique, in particular mutually perpendicular.

4. Electrical energy storage device according to one of the preceding claims, in which each of the free spaces (33, 43) opens, via a first end (331, 431), onto the front receiving face (51) of the support and, via a second end (332, 432), opposite said front receiving face, said first end (331, 431) of each free space (33, 43) being advantageously located at a distance from the electrical contact member (60, 61) adjacent to this first end.

5. Electrical energy storage device according to one of the preceding claims, in which each electrical contact member (60, 61) is capable of providing an additional function of mechanical connection between the storage module and the support, the electrical contact member being advantageously made of a conductive adhesive material.

6. Electrical energy storage device according to one of the preceding claims, in which the electrical contact member has a thickness (e60) of less than 100 pm (microns).

7. Electrical energy storage device according to one of claims 2 to 6, in which the free space (2033) of each first electrode, or of each second electrode, comprises a through branch (2330) connecting the longitudinal edges of said electrode as well as an auxiliary branch (2331) connecting the through branch with the transverse edge (2304) opposite said electrode, the auxiliary branch separating the main body (2031) from a so-called tertiary body (2035) while the through branch separates the secondary body (2032) from both the main body and the tertiary body.

8. Electrical energy storage device according to one of the claims- preceding indications, wherein each first electrode is a first polarity electrode, while each second electrode is a second polarity electrode.

9. Electrical energy storage device according to the preceding claim, in which this device is a battery, the separator being made of an electronically insulating but ionically conductive material, the energy storage module further comprising a liquid electrolyte impregnating at least part of the electrodes and / or the separator.

10. Energy storage device according to claim 8, wherein this device is a pseudo-capacitor, a lithium ion hybrid supercapacitor, a sodium ion hybrid supercapacitor, a potassium ion hybrid supercapacitor, lithium ion batteries, sodium ion batteries, potassium ion batteries, the separator being made of an electronic insulating material but conductive of electrical charges.

11. An electrical energy storage device according to one of claims 1 to 7, wherein this device is a capacitor, preferably chosen from a Metal-Insulator-Metal (MIM) type capacitor and multilayer capacitors, each first electrode and each second electrode being a current collector.

12. Electrical energy storage device according to one of the preceding claims, further comprising a mechanical protection system (608; 708), providing mechanical protection at least with respect to the storage module.

13. Energy storage device according to one of the preceding claims, further comprising an encapsulation system (7; 607), in particular merged with the mechanical protection system, the encapsulation system ensuring protection with respect to the sealing of both the storage module and the electrical connection support, in which said encapsulation system (7) advantageously covers the opposite front faces (21, 22) of the storage module, the lateral face (24) of the storage module opposite the lateral contact face, the other two lateral faces (25, 26) of the storage module, at least in part the first electrical contact member (60), at least in part the second electrical contact member (61), as well as at least in part the receiving face (51) of said electrical connection support (5).

14. Electrical energy storage device according to the preceding claim, further comprising a mechanical stiffening system (8), covering the encapsulation system opposite the electrical connection support (5).

15. Method for manufacturing an electrical energy storage device according to one of the preceding claims, said method comprising: - the relative positioning of the energy storage module (2) and the electrical connection support (5), substantially in the final position that they must adopt - the electrical connection of each first electrode (3) with the first electrical connection region (58) of the support - the electrical connection of each second electrode (4) with the second electrical connection region (59) of the support - possibly the impregnation of the energy storage module by means of the electrolyte - possibly the coating of the encapsulation system (7).

16. Method according to the preceding claim, comprising - providing a blank (2') not impregnated with electrolyte, said blank being intended to form the energy storage module - the relative positioning of the blank and the electrical connection support - impregnating the blank with the electrolyte, so as to form the energy storage module.

17. Method according to the preceding claim, in which at least a portion (509) of said electrolyte is introduced via the second end (332, 432) of said free spaces, and in which the blank is advantageously impregnated by causing the electrolyte to flow by gravity (G509, H509).

18. An electrical energy consuming assembly (1000) comprising a body (1002), an energy consuming element (1004) and at least one electrical energy storage device (1) according to one of claims 1 to 14, said electrical energy storage device (1) being capable of supplying electrical energy to said electrical energy consuming element (1004), and said electrical connection support (5) of said electrical energy storage device being fixed to said body.

19. An energy consuming assembly according to claim 18, comprising at least two energy storage devices which are placed on a single electrical connection support and are connected in series and / or in parallel, said at least two energy storage devices being advantageously covered by means of a single encapsulation system, or a single mechanical protection system.

20. Energy consuming assembly according to claim 18, comprising an additional electronic component, placed on a single electrical connection support with the electrical energy storage device, this electronic component and this energy storage device being advantageously covered by means of a single encapsulation system, or else a single mechanical protection system.

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