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    • 专利摘要:
    Encapsulation system (30) for an object such as an electronic component or a battery, characterized in that it is formed by three successive layers comprising (iv) a first covering layer (31,31 ') composed of an electrically insulating material deposited by ALD (Atomic Layer Deposition), which at least partially covers said object, (v) a second covering layer (32,32 ') comprising parylene, arranged on the first covering layer (vi) a third cover layer (33,33 ') deposited on the second cover layer so as to protect the second encapsulation layer, in particular oxygen, and to increase the lifetime of the object.
    公开号:FR3068830A1
    申请号:FR1756364
    申请日:2017-07-06
    公开日:2019-01-11
    发明作者:Fabien Gaben
    申请人:I TEN；
    IPC主号:
    专利说明:

    Encapsulation system for electronic components and batteries
    Technical field of the invention
    The present invention relates to systems for encapsulating objects such as microelectronic components and batteries. It relates more particularly to the field of batteries, and in particular lithium ion batteries, which can be encapsulated in this way. The invention also relates to a new method for manufacturing thin-film lithium ion batteries, having a new architecture and encapsulation which gives them a particularly low self-discharge, and an improved lifetime.
    State of the art
    Microelectronic components and batteries, and in particular thin film batteries, must be encapsulated to be durable as oxygen and humidity degrade them. In particular, lithium ion batteries are very sensitive to humidity, and need an encapsulation which ensures a lifespan of more than 10 years. With the spread of portable electronic devices and autonomous sensor networks, the need for rechargeable batteries with high energy density and high power density has increased considerably. Thin-film Li-ion batteries have a high energy density and a high power density, are rechargeable, and have no memory effect: they are capable of satisfying this need, but their reliability and their lifespan remain critical factors.
    Thin-film Li-ion batteries include electrodes and an entirely solid electrolyte, that is to say liquid-free. The thickness of the various layers which constitute them normally does not exceed 10 µm, and is often between 1 and 4 µm. It is observed that these thin-film batteries such as multilayer batteries are sensitive to self-discharge. Depending on the positioning of the electrodes, in particular the proximity of the edges of the electrodes for multilayer batteries and the cleanliness of the cutouts, a leakage current may appear on the ends, a creeping short circuit which reduces the performance of the battery. This phenomenon is exacerbated if the electrolyte film is very thin.
    These fully solid thin-film Li-ion batteries most often use anodes with a layer of metallic lithium. It is observed that the anode materials exhibit a large variation in their volume during the charge and discharge cycles of the battery. Indeed, during a charge and discharge cycle, part of the metallic lithium is transformed into lithium ions which are inserted into the structure of the cathode materials, which is accompanied by a reduction in the volume of the 'anode. This cyclic variation in volume can deteriorate the mechanical and electrical contacts between the electrode and electrolyte layers. This decreases the performance of the battery during its life.
    The cyclic variation in the volume of the anode materials also induces a cyclic variation in the volume of the battery cells. It thus generates cyclic stresses on the encapsulation system, capable of initiating cracks which are at the origin of the loss of tightness (or even of integrity) of the encapsulation system. This phenomenon is another cause of the decrease in battery performance during its life
    Indeed, the active materials of Li-ion batteries are very sensitive to air and in particular to humidity. The mobile lithium ions react spontaneously with traces of water to form LiOH, inducing a calendar aging of the batteries. Not all insertion materials and electrolytes that conduct lithium ions are reactive on contact with moisture. For example, Li 4 Ti 5 0i 2 does not deteriorate on contact with the atmosphere or traces of water. On the other hand, as soon as it is charged with lithium in the form υ 4 + χ Τί 5 0ι 2 with x> 0, then the surplus of lithium inserted (x) is, meanwhile, sensitive to the atmosphere and reacts spontaneously with traces of water to form LiOH. The reacted lithium is then no longer available for storing electricity, leading to a loss of battery capacity.
    To avoid exposure of the active materials of the Li-ion battery to air and water and to prevent this type of aging, it is essential to protect it with an encapsulation system. Many encapsulation systems for thin film batteries are described in the literature.
    Document US 2002/0 071 989 describes a system for encapsulating a fully solid thin film battery comprising a stack of a first layer of a dielectric material chosen from alumina (AI 2 O 3 ), silica (SiO 2 ), silicon nitride (Si 3 N 4 ), silicon carbide (SiC), tantalum oxide (Ta 2 O 5 ) and amorphous carbon, of a second layer of a dielectric material and a sealing layer disposed on the second layer and covering the entire battery.
    Document US 5,561,004 describes several protection systems for a thin-film lithium battery. A first system proposed comprises a layer of parylene covered with an aluminum film deposited on the active components of the battery.
    However, this protection system against the diffusion of air and water vapor is only effective for about a month. A second proposed system includes alternating layers of parylene (500 nm thick) and metal (approximately 50 nm thick). The document specifies that it is preferable to coat these batteries still with a layer of epoxy cured with ultraviolet (UV) so as to reduce the rate of degradation of the battery by atmospheric elements.
    According to the state of the art, most Li-ion batteries are encapsulated in metallized polymer sheets (called "pouch") closed around the battery cell and heat sealed at the level of ribbons (called "tabs"). These packages are relatively flexible and the positive and negative connections of the battery are then embedded in the heat-sealed polymer which was used to close the packaging around the battery. However, this weld between the polymer sheets is not completely impermeable to gases from the atmosphere, the polymers used to heat-seal the battery are fairly permeable to gases from the atmosphere. It is observed that the permeability increases with temperature, which accelerates aging.
    However, the surface of these solders exposed to the atmosphere remains very small, and the rest of the packaging consists of aluminum sheets sandwiched between these polymer sheets. In general, two aluminum sheets are combined in order to minimize the effects linked to the presence of holes, of defects in each of these aluminum sheets. The probability that two faults on each of the strips are aligned is greatly reduced.
    These packaging technologies guarantee around 10 to 15 years of calendar life for a 10 Ah battery with a surface area of 10 x 20 cm 2 , under normal conditions of use. If the battery is exposed to a high temperature, this lifespan can be reduced to less than 5 years; this remains insufficient for many applications. Similar technologies can be used for other electronic components, such as capacitors, active components.
    Accordingly, there is a need for systems and methods for encapsulating thin film batteries and other electronic components, which protect the component from air, humidity and the effects of temperature. More particularly there is a need for systems and methods for encapsulating lithium ion batteries in thin layers, which protects them against air and humidity as well as against their deterioration when the battery is subjected to charge cycles. and discharge. The encapsulation system must be watertight and hermetic, must completely wrap and cover the component or the battery, must be flexible enough to be able to accompany slight changes in size ("breaths") of the battery cell, and must also allow separation galvanically the edges of electrodes of opposite signs to avoid any creeping short circuit.
    An objective of the present invention is to remedy at least in part the drawbacks of the prior art mentioned above.
    Another objective of the present invention is to provide lithium ion batteries with a very long service life and having a low self-discharge.
    Objects of the invention
    The present invention proposes as a first object a system for encapsulating an object such as an electronic component or a battery, characterized in that it is formed by three successive layers comprising
    i. a first covering layer 31, 31 ’composed of an electrically insulating material deposited by ALD (Atomic Layer Déposition), which at least partially covers said object, ii. a second covering layer 32, 32 ’comprising parylene, disposed on the first covering layer, iii. a third covering layer 33, 33 ’deposited on the second covering layer so as to protect the second encapsulation layer, in particular from oxygen and to increase the life of the object.
    Advantageously, the encapsulation system of an object comprises a covering layer comprising parylene, preferably parylene N and an encapsulation system (30) deposited on said covering layer comprising parylene.
    A second object is an electronic component or a battery, preferably a thin-film battery comprising an encapsulation system 30.
    Another object is a thin film battery comprising an alternating stack between at least one anode 10, 10 'and at least one cathode 20, 20', each consisting of a stack of thin layers and in which the anode 10, 10 'comprises o at least one thin layer of an anode active material 12, and o optionally a thin layer of an electrolyte material 13, and in which stack the cathode 20, 20' comprises o at least one thin layer of an active cathode material 22, and optionally a thin layer of an electrolyte material 23 so that the battery successively comprises at least one thin layer of an active anode material 12, at least one thin layer of an electrolyte material 13,23 and at least one thin layer of an active cathode material 22, an encapsulation system 30 in which said first layer 31,31 'at least partially covers the stack, said encapsulation system 30 recou partially facing said stack, a first anode 10 or cathode 20 comprising at least one accessible connection zone, while the cathode 20 or the adjacent anode 10 comprises a covering zone ZRT, which is covered by at least said first covering layer (31,3T) and said second covering layer (32,32 '), said covering zone being situated opposite the connection zones ZC of the first anode or cathode, in a direction perpendicular to the plane of said stack.
    Another object of the invention is a method of manufacturing an electronic component or an encapsulated battery, comprising the formation of an encapsulation system 30 and in which one deposits successively so as to form said system encapsulation 30:
    (i) a first covering layer 31.31 ′ composed of an electrically insulating material by ALD (Atomic Layer Déposition), (ii) a second covering layer 32.32 ′ comprising parylene, deposited on said first covering layer , (iii) a third covering layer 33, 33 ′, deposited on the second covering layer, suitable for, and deposited so as to protect the second encapsulation layer, in particular from oxygen.
    Another object of the invention is a method of manufacturing an electronic component or an encapsulated battery, comprising the formation of an encapsulation system according to the invention and in which one deposits successively so as to forming said encapsulation system:
    a covering layer comprising parylene on said electronic component or said battery a first covering layer (31.3T) composed of an electrically insulating material by ALD (Atomic Layer Deposition) deposited on said covering layer comprising parylene, a second covering layer (32,32 ') comprising parylene, deposited on said first covering layer, a third covering layer (33,33'), deposited on the second covering layer, suitable for, and deposited so, protect the second encapsulation layer, in particular from oxygen.
    Yet another object of the invention is a method of manufacturing a thin-film battery, said battery comprising an alternating stack between at least one anode 10, 10 'and at least one cathode 20, 20', each consisting of a stack of thin layers and in which the anode 10, 10 ′ comprises, o at least one thin layer of an active anode material 12, and o optionally a thin layer of an electrolyte material 13, and in which the cathode 20, 20 'comprises o at least one thin layer of an active cathode material 22, and o optionally a thin layer of an electrolyte material 23 so that the battery successively comprises at least one thin layer d an active anode material 12, at least one thin layer of an electrolyte material 13,23 and at least one thin layer of an active cathode material 22, said method comprising the following steps:
    (A) a primary superposition is formed, comprising an alternating succession of cathode sheets and anode sheets, said primary superposition being intended to form at least one battery, two adjacent sheets defining at least one protruding region RS, intended for forming said accessible connection zone ZC, as well as at least one recessed region RT, intended to form said overlapping zone RTC, (b) the encapsulation system according to the invention is deposited by the method described above.
    Advantageously, after step (b), the accessible connection area ZC or each accessible connection area ZC is displayed.
    In one embodiment, after step (b), a step (c) is carried out comprising at least one primary cut perpendicular to the plane of said primary superposition so as to make a connection zone ZC accessible at the level of the anode. hereinafter anodic connection zone and at least one primary cut is made perpendicular to the plane of said primary superposition so as to make a connection zone ZC accessible at the cathode hereinafter cathodic connection zone.
    Advantageously, the primary cuts are made at opposite edges of said primary superposition.
    In a first embodiment, the edges of the two adjacent sheets of the primary overlay comprising an alternating succession of cathode sheets and anode sheets are straight edges, the edge of a first sheet forming the protruding region RS then as the edge of a second sheet forming the recessed region RR.
    In a second embodiment, in the edge of a first sheet of the primary overlay comprising an alternating succession of cathode sheets and anode sheets, first notches 50, 50 ', 50 ", 50"' having a first or large section, the wall of said first notches constituting said recessed region, and there is produced, in a second adjacent sheet, second notches having a second or small section, smaller than the first section, the wall of said second notches 50, 50 ', 50 ”, 50'” constituting said protruding region RS.
    Advantageously, the cathode sheets and the anode sheets have notches 50, 50 ’, 50”, 50 ’” in the shape of a circle.
    Advantageously, first holes are made in a first sheet having a first or large section, the wall of said holes constituting said recessed region, second holes are made in a second adjacent sheet having a second or small section, lower in the first section, the wall of said orifices constituting said protruding region RS, the interior volume of said orifices is filled by means of the encapsulation system and each secondary cut is made inside said first and second orifices, so that the ZC connection zones are formed in the vicinity of the walls having the small section and the overlap zones are formed in the vicinity of the walls having the large section.
    Advantageously, in two adjacent sheets, first and second slots are produced, mutually offset in the direction perpendicular to the plane of said sheets, the interior volume of said slots is filled by means of the encapsulation system and each secondary cutting is carried out. inside said slots, so that the connection zones are formed in the vicinity of the walls of a first slot and the overlap zones are formed in the vicinity of the walls of a second slot.
    Advantageously, after step (c), the anode and cathode connection zones ZC are electrically connected to each other by a thin layer deposition of an electronic conductor and in which the deposition is carried out by ALD 41, 41 ’.
    Advantageously, 40, 40 ′ anodic and cathodic terminations are produced by metallization of the sections previously covered with a thin layer of an electronic conductor.
    Advantageously, after step (c), the anode and cathode connection zones are electrically connected to each other by a termination system successively comprising:
    o an optional first metallic layer, preferably deposited by ALD 41, 41 ′, o a second layer 42, 42 ′ based on silver-charged epoxy resin, deposited on the first metallic layer, and o a third layer 43, 43 'based on tin, deposited on the second layer.
    In another embodiment, after step (c), the anode and cathode connection zones are electrically connected to each other by a termination system successively comprising:
    o a first metallic layer, optional, preferably deposited by ALD (41), o a second layer (42) based on silver-charged epoxy resin, deposited on the first metallic layer, and o a third layer (43a) based on nickel, deposited on the second layer, o a fourth layer (43b) based on tin or copper, deposited on the third layer.
    Advantageously, the sheets have dimensions significantly greater than those of the final battery, characterized in that at least one other so-called secondary cutting is made, in a middle part of said sheets.
    Advantageously, said electrically insulating material is chosen from organic or inorganic non-conductive polymeric materials having barrier properties with respect to water. Advantageously, said electrically insulating material is chosen from Al 2 O 3 , SiO 2 , SiO y N x and epoxy resins.
    Advantageously, the second covering layer comprises parylene N.
    Advantageously, the thickness of the first thin covering layer is less than 200 nm, preferably between 5 nm and 200 nm, and even more preferably around 50 nm and the thickness of the second covering layer is between 1 pm and 50 pm, preferably about 10 pm.
    Advantageously, the thickness of the third thin covering layer is between 1 μm and 50 μm, preferably less than 10 μm, preferably less than 5 μm and even more preferably around 2 μm.
    Advantageously, the layer of anode material is produced from a material chosen from:
    (i) tin oxynitrides (of typical formula SnO x N y );
    (ii) lithiated iron phosphate (of typical formula LiFePO 4 );
    (iii) mixed oxynitrides of silicon and tin (of typical formula Si a Sn b O y N z with a> 0, b> 0, a + b <2, 0 <y <4, 0 <z <3) ( also called SiTON), and in particular SiSn 0 , 87Oi, 2N 1 , 72; as well as the oxynitride-carbides of typical formula Si a Sn b C c O y N z with a> 0, b> 0, a + b <2, 0 <c <10, 0 <y <24, 0 <z <17; If a Sn b C c O y N z X n with X at least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb and a> 0, b> 0, a + b> 0, a + b <2, 0 <c <10, 0 <y <24 and 0 <z <17; and Si a Sn b O y N z X n with X n at least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb and a> 0, b> 0, a + b <2, 0 <y <4 and 0 <z <3;
    (iv) nitrides of type Si x N y (in particular with x = 3 and y = 4), Sn x N y (in particular with x = 3 and y = 4), Zn x N y (in particular with x = 3 and y = 4), Li 3 . x M x N (with M = Co and 0 <x <0.5, with M = Ni and 0 <x <0.6 or with M = Cu and 0 <x <0.3);
    (v) the oxides SnO 2 , Li 4 Ti 5 0i 2 , SnBo, 6 Po, 4 0 2 , 9 and TiO 2 .
    Advantageously, the layer of electrolyte material is produced from electrolyte material chosen from:
    o garnets of formula Li d A 1 x A 2 y (TO 4 ) z where
    A 1 represents a cation of oxidation state + II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and or
    A 2 represents a cation of oxidation state + III, preferably Al, Fe, Cr, Ga, Ti, La; and where (TO 4 ) represents an anion in which T is an atom of degree of oxidation + IV, located at the center of a tetrahedron formed by the oxygen atoms, and in which TO 4 advantageously represents the silicate anion or zirconate, knowing that all or part of the elements T of an oxidation state + IV can be replaced by atoms of an oxidation state + III or + V, such as Al, Fe, As, V, Nb, ln, Ta;
    knowing that: d is between 2 and 10, preferably between 3 and 9, and even more preferably between 4 and 8; x is 3 but can be between 2.6 and 3.4 (preferably between 2.8 and 3.2); y is 2 but can be between 1.7 and 2.3 (preferably between 1.9 and 2.1) and z is 3 but can be between 2.9 and 3.1;
    o garnets, preferably chosen from: Li 7 La 3 Zr 2 0i 2 ; Li6La 2 BaTa 2 0i2; the Li55La 3 Nb 17 5lno. 2 50i 2 ; Ι_ί 5 Ι_3 3 Μ 2 0ι 2 with M = Nb or Ta or a mixture of the two compounds; the U 7 . x Ba x La 3 . x M 2 0i 2 with 0 <x <1 and M = Nb or Ta or a mixture of the two compounds; the Li 7 . x La 3 Zr 2 . x M x Oi 2 with 0 <x <2 and M = Al, Ga or Ta or a mixture of two or three of these compounds;
    o lithiated phosphates, preferably chosen from: Li 3 PO 4 ; Li 3 (Sc 2. x M x ) (PO 4 ) 3 with M = AI or Y and 0 <x <1; Li 1 + x M x (Sc) 2 . x (PO 4 ) 3 with M = Al, Y, Ga or a mixture of the three compounds and 0 <x <0.8; Li 1 + x M x (Ga 1. y Sc y ) 2 . x (PO 4 ) 3 with 0 <x <0.8; 0 <y <1 and M = Al or Y or a mixture of the two compounds; Li 1 + x M x (Ga) 2 . x (PO 4 ) 3 with M = Al, Y or a mixture of the two compounds and 0 <x <0.8; Li 1 + x Al x Ti 2 . x (PO 4 ) 3 with 0 <x <1, or Li 1 + x Al x Ge 2 . x (PO 4 ) 3 with 0 <x <1; or Liux + zM ^ GevyTiyj ^ xSizPs-zO ^ with 0 <x <0.8 and 0 <y <1.0 & 0 <z <0.6 and M = Al, Ga or Y or a mixture of two or three of these compounds; Li 3 + y (Sc 2. x M x ) Q y P 3 . γ Οι 2 , with M = Al and / or Y and Q = Si and / or Se, 0 <x <0.8 and 0 <y <1; or Li 1 + x + y M x Sc 2 . x QyP 3 .yOi 2 , with M = Al, Y, Ga or a mixture of the three compounds and Q = Si and / or Se, 0 <x <0.8 and 0 <y <1; or Lh + x + y + zM ^ Ga ^ ySCy ^ .xQzPs.zO ^ with 0 <x <0.8; 0 <y <1; 0 <z <0.6 with M = Al or Y or a mixture of the two compounds and Q = Si and / or Se; or Li 1 + x N x M 2 . x P 3 0i 2 , with 0 <x <1 and N = Cr and / or V, M = Sc, Sn, Zr, Hf, Se or Si, or a mixture of these compounds;
    o the lithium-containing sulfur compounds, preferably chosen from: Li x Al z .yGa y S w (PO 4 ) c with 4 <w <20, 3 <x <10, 0 ^ y <1, 1 ^ z <4 and 0 <c <20; Li x Al z .yGa y S w (BO 3 ) c with 4 <w <20, 3 <x <10, 0 ^ y <1, 1 ^ z <4 and 0 <c <20; Li x Al z .ySc y S w (PO 4 ) c with 4 <w <20, 3 <x <10, 0 ^ y <1, 1 ^ z <4 and 0 <c <20; Li x Al z .ySc y S w (BO 3 ) c with 4 <w <20, 3 <x <10, 0 ^ y <1, 1 ^ z <4 and 0 <c <20; Li x Ge z .ySiyS w (PO 4 ) c with 4 <w <20, 3 <x <10, 0 ^ y <1, 1 ^ z <4 and 0 <c <20; Li x Ge ( zy) SiyS w (BO 3 ) c with 4 <w <20, 3 <x <10, 0 ^ y <1, 1 ^ z <4 and 0 <c <20;
    o the lithiated borates, preferably chosen from: Li 3 (Sc 2. x M x ) (BO 3 ) 3 with M = AI or Y and 0 <x <1; Li 1 + x M x (Sc) 2 . x (BO 3 ) 3 with M = Al, Y, Ga or a mixture of the three compounds and 0 <x <0.8; 0 <y <1; LiuxM ^ GavySCyj ^ BO ^ s with 0 <x <0.8;
    <y <1 and M = Al or Y; Li 1 + x M x (Ga) 2 . x (BO 3 ) 3 with M = Al, Y or a mixture of the two compounds and 0 <x <0.8; 0 <y <1; Li 3 BO 3 , Li 3 BO 3 -Li 2 SO 4 , Li 3 BO 3 -U 2 SiO 4 , Li 3 BO 3 -Li 2 SiO 4 -Li 2 SO 4 ;
    o oxynitrides, preferably chosen from Li 3 PO 4 . x N 2x / 3 , Li 4 SiO 4 . x N 2x / 3 , Li 4 GeO 4 . x N 2x / 3 with 0 <x <4 or Li 3 BO 3 . x N 2x / 3 with 0 <x <3; materials based on lithium oxynitrides of phosphorus or boron (called LiPON and LIBON) which may also contain silicon, sulfur, zirconium, aluminum, or a combination of aluminum, boron, sulfur and / or silicon, and boron for lithium phosphorus;
    o lithiated oxides, preferably chosen from Li 7 La 3 Zr 2 0i 2 or Li 5 + x La 3 (Zr x , A 2. x ) Oi2 with A = Sc, Y, Al, Ga and 1,4 <x <2 or Li 0, 3 0 5The, 55TiO 3;
    o silicates, preferably chosen from Li 2 Si 2 O5, Li 2 SiO 3 , Li 2 Si 2 O6, LiAISiO 4 , Li 4 SiO4, LiAISi 2 O 6 ;
    o solid electrolytes of anti-perovskite type chosen from:
    Li 3 OA with A a halide or a mixture of halides and preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these elements;
    Lip.xjMxœOA with 0 <x <3, M a divalent metal, preferably at least one of the elements chosen from Mg, Ca, Ba, Sr or a mixture of two or three or four of these elements, A halide or a mixture halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these elements;
    υ ^ Ν, ^ ΟΑ with 0 <x <3, N a trivalent metal, A a halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these;
    LiCOX z Y (i_ Z ), with X and Y halides and 0 <z <1;
    o electrolytes based on polymers conducting lithium ions impregnated or not with lithium salts, o hybrid electrolytes comprising an inorganic matrix such as a ceramic matrix in which an organic electrolyte comprising lithium salts is inserted.
    Yet another object of the invention is a thin-film battery capable of being obtained by the method according to the invention.
    Yet another object of the invention is a thin-film battery capable of being obtained by the method according to the invention characterized in that said encapsulation system completely covers four of the six faces of said battery and partially the two remaining faces laterally opposite, said two remaining faces being partially coated with at least said first covering layer (31.3T) and at least said second layer (32.32 ') and said two remaining faces comprising an anodic connection zone and a cathodic connection area.
    Another object of the invention is a battery comprising an alternating stack between at least one anode 10 'and at least one cathode 20', each consisting of a stack of thin layers and in which the anode 10 'comprises, o at at least one thin layer of active anode material 12 ', and optionally a thin layer of electrolyte material 13', and in which the cathode 20 'comprises o at least one thin layer of active material cathode 22 ', and optionally a thin layer of an electrolyte material 23' so that the battery successively comprises at least one thin layer of an active anode material, at least one thin layer of a material of electrolyte and at least one thin layer of an active cathode material, it being understood that the anode 10 'has a first orifice 50 having a first section, the wall of said first orifice constituting at least one recessed region RT (respectively protruding RS) and the adjacent cathode 20 ′ has a second orifice having a second section, lower (respectively upper) than the first section, the wall of said second orifice constituting at least one protruding region RS (respectively set back RT); said at least protruding region defining an accessible connection area ZC and said at least recessed region RT defining an inaccessible overlap area.
    figures
    Figures 1 to 27 illustrate certain aspects of the invention, but do not limit its scope.
    Figure 1 shows schematically, a battery showing a central element and terminations arranged at the two ends of the central element.
    FIG. 2 represents a perspective view with cutaway along line II-II of an entirely solid battery, showing the internal structure of the central element comprising an assembly of elementary cells covered by an encapsulation system according to the invention and that of the endings.
    Figure 3 is a perspective view with cutaway similar to Figure 2 illustrating on a larger scale the detail III of this figure 2. The constituent elements of the elementary cells, the encapsulation system and the terminations are presented in greater detail respectively in Figures 4, 5 and 6.
    Figure 4 is a perspective view with cutaway similar to Figure 3 illustrating on a larger scale the detail IV of this Figure 3, illustrating the internal structure of different components of an entirely solid battery.
    Figure 5 is a perspective view with cutaway similar to Figure 4 illustrating on a larger scale the internal structure of the encapsulation system according to the invention.
    Figure 6 is a perspective view with cutaway similar to Figure 4 illustrating on a larger scale the internal structure of the terminations.
    FIG. 7 represents an exploded perspective view of the stack of thin layers of anode and cathode, so that these layers are offset laterally.
    FIG. 8 represents an exploded perspective view of the encapsulation system according to the invention of the stack of anode and cathode layers comprising a stack of cover layers.
    FIG. 9A represents a view at the outlet of the anode showing the anode current collectors surrounded on their periphery by the encapsulation system. FIG. 9B represents a view at the output of the cathode showing the cathode current collectors surrounded on their periphery by the encapsulation system.
    Figure 10 shows an exploded perspective view of the terminations of an entirely solid battery, made up of a stack of layers.
    FIG. 11 schematically represents the method of manufacturing several entirely solid batteries from an alternative stack of sheets comprising between several tens and several hundreds of anodes delimited along a U-shaped cutting plane and of sheets comprising between several tens and several hundred cathodes delimited along a U-shaped cutting plane.
    FIG. 12 represents a perspective view with cutaway of an entirely solid battery, according to line XII-XII of FIG. 11 showing the stack of sheets of anodes and cathodes superimposed and offset laterally.
    FIG. 13 represents a perspective view with cutaway of an entirely solid battery, according to line XIII-XIII of FIG. 11 showing the stack of sheets of anodes and cathodes superimposed and offset laterally.
    FIG. 14 represents a perspective view with cutaway of an entirely solid battery showing the stacking of the sheets of anodes and cathodes superimposed and offset laterally, as well as the encapsulation system and the terminations.
    FIG. 15 represents a perspective view with cutaway similar to FIG. 14 illustrating on a larger scale the detail VI of this FIG. 14, illustrating the internal structure of different elements constituting an entirely solid battery.
    FIG. 16 schematically represents, according to another embodiment, the method of manufacturing several entirely solid batteries.
    FIG. 17 schematically represents a sectional view illustrating on a larger scale the detail VII of FIG. 16.
    FIG. 18 represents a perspective view similar to FIG. 16 illustrating on a larger scale the detail VIII of this FIG. 16.
    FIG. 19A represents a perspective view with cutaway of an entirely solid battery, along line XIX-XIX of FIG. 18. FIG. 19B represents a perspective view with cutaway of an entirely solid battery, along line XIX ' -XIX 'of figure 18.
    FIG. 20 represents a perspective view of the structure presented in FIG. 18 covered with the encapsulation system.
    FIG. 21A represents a perspective view with cutaway of an entirely solid battery, along line XXI-XXI of FIG. 20. FIG. 21B represents a perspective view with cutaway of an entirely solid battery, along line XXI ' -XXI 'of figure 20.
    FIG. 22 represents a perspective view similar to FIG. 21A illustrating on a larger scale the detail IX of this FIG. 21A.
    FIG. 23 represents a perspective view similar to FIG. 22 illustrating on a larger scale the detail X of this FIG. 22.
    FIG. 24 represents a perspective view of the structure presented in FIG. 20 and showing the multilayer encapsulation system according to the invention covered with the multilayer system of terminations.
    FIG. 25 represents a perspective view with cutaway of an entirely solid battery, according to the line XXV-XXV or XXV'-XXV ’in FIG. 24 showing the stack of superimposed sheets of anodes and cathodes.
    Figure 25A shows the anode contacts laterally covered by the multilayer termination system.
    FIG. 25B shows the cathode contacts covered laterally by the multilayer system of terminations.
    FIG. 26 represents a perspective view similar to FIG. 25 illustrating on a larger scale the detail XI of this FIG. 25.
    FIG. 27 represents a perspective view similar to FIG. 26 illustrating on a larger scale the detail XII of this FIG. 26.
    List of references used in the figures:
    1 Fully solid battery 23, 23 ’ Thin layer of electrolyte material 2 Elementary cell 30, 30 ’ Encapsulation system according to the invention 3 Stack of anode and cathode sheets 31, 31 ’ 1 st thin covering layer 10, 10 ’ Anode 32/33 2 nd / 3 rd covering layer 11, 11 ’ Thin layer of a conductive substrate such as stainless steel 40, 40 ’ terminations 12, 12 ’ Thin layer of active anode material 41, 41 ’ Metallic layer deposited by ALD 13, 13 ’ Thin layer of electrolyte material 42, 42 ’ Epoxy resin layer loaded with Ag 20, 20 ’ Cathode 43, 43 ’ Metallization layer (tin) 21, 21 ’ Thin layer of a conductive substrate such as stainless steel 43a /43b First / second metallization layer
    22, 22 ’ Thin layer of cathode active material F Arrow indicating the areas covered by the encapsulation system RS Projecting region RR Set back region ZRT overlap area ZC connection areas III, IV, V, VI, VII, VIII, IX, X, XI, XII magnifications ll-ll, XII-XII, XIX-XIX, XIX’-XIX ’, XXI-XXI, XXI’-XXI’, XXV-XXV, XXV’-XXV ’ Axis
    Description of the invention
    The present invention relates to a system for encapsulating an object giving it electrical insulation and protecting it from the external environment, and in particular from the ambient atmosphere. The encapsulation system according to the invention makes it possible to offer protection adapted to the constraints that the electronic components must effectively be able to withstand without significant disturbance of their operation or without damage.
    The system for encapsulating an object according to the invention comprises:
    i. a first covering layer composed of an electrically insulating material deposited by ALD (Atomic Layer Déposition) intended to cover at least partially said object, ii. a second layer comprising parylene disposed on the first covering layer, iii. a third layer deposited on the second covering layer so as to protect the second encapsulation layer, in particular from oxygen and to increase the lifespan of the object.
    The encapsulated object can be an electronic component (such as an integrated circuit, a resistor, a capacitor), a battery, a photovoltaic panel.
    The first covering layer 31 of the encapsulation system consists of an electrically insulating material such as AI 2 O 3 , SiO 2 , SiO y N x and epoxy resins. Advantageously, said electrically insulating material is chosen from organic or inorganic polymeric materials having barrier properties with respect to water. This layer is deposited on at least part of said object by an atomic layer deposition process (Atomic layer deposition in English, better known by the acronym ALD). When the object is a battery, the first covering layer 31 is deposited on the primary stack or overlay by ALD. The ALD deposition techniques are particularly well suited for covering surfaces with high roughness in a completely waterproof and conforming manner. The ALD deposition techniques allow conformal deposition, free from defects and holes. These deposits are qualified as “pinhole free” and represent very good barriers. Their WVTR coefficient is extremely low. The WVTR (water vapor transmission rate) coefficient makes it possible to assess the water vapor permeance of the encapsulation system. The lower the WVTR coefficient, the more waterproof the encapsulation system. For example, a deposit of AI 2 O 3 100 nm thick by ALD has a water vapor permeation of 0.00034 g / m2.d.
    The first encapsulation layer thus obtained generally consists of oxides, of the AI 2 O 3 type , of nitride, of phosphates, of oxynitride, of siloxane, of a thickness less than 200 nm, preferably between 5 nm. and 200 nm, more preferably between 10 nm and 100 nm and even more preferably of the order of fifty nanometers. However, these layers are very fragile mechanically and require a rigid support surface. The deposition of a fragile layer on a flexible surface would lead to the formation of cracks, causing a loss of integrity of this protective layer. Furthermore, to allow a relatively high deposition rate industrially, these layers must be deposited at a fairly high temperature, ie at a temperature between 180 ° C. and 300 ° C. The materials constituting the object must thus resist such temperatures and have a sufficiently rigid surface to guarantee the achievement of a quality encapsulation by ALD. This applies in particular to stacks of the Li-ion battery. However, most of the usual electrolytes based on polymers containing lithium salts, ie electrolytes in the form of gel, liquids or containing pockets of liquid, do not withstand such a temperature and do not have a sufficiently rigid surface to guarantee achieving reliable encapsulation by ALD. In fact, under vacuum and at high temperature, these electrolytes degas and thus prevent the production of thin homogeneous and protective deposits directly on their surfaces. Preferably, therefore, the use of these electrolytes in batteries which will benefit from the encapsulation system according to the invention will be avoided.
    When the object is a battery, this first encapsulation layer also makes it possible to separate the sections of the electrodes, in order to reduce the self-discharge and the risks of aging of the battery, which thus facilitates the bringing together of the electrodes.
    According to the invention, a second encapsulation layer 32 is deposited on the first encapsulation layer in order to improve the protection of the object (i.e. electronic component such as a battery) from its external environment. This layer is made of parylene. Parylene (also called polyparaxylylene or poly (p-xylylene)) is a dielectric, transparent, semi-crystalline material which has high thermodynamic stability, excellent resistance to solvents and very low permeability. In one embodiment, a parylene film is deposited on the first layer, such as a film of parylene C, of parylene D, a film of parylene N (CAS 163322-3) or a film comprising a mixture of parylene C, D and / or N. This parylene film protects the sensitive elements of the object from their environment. The protection of the battery is increased when this second encapsulation layer is produced from parylene N. The thickness of said second encapsulation layer is between 1 μm and 50 μm, preferably between 1 μm and 35 μm and even more preferably around 10 μm.
    This second encapsulation layer is advantageously obtained from the condensation of gaseous monomers deposited by chemical vapor deposition (CVD) on the surfaces, which makes it possible to have a conformai and uniform covering of all the surfaces of the accessible object.
    This second layer ensures the filling of the encapsulation system without degrading the first layer of the encapsulation system. It makes it possible to follow the variations in volume of the object during its operation and facilitates the clean cutting of the batteries due to its elastic properties. However, the inventors have observed that this second layer does not have sufficient stability in the presence of oxygen. According to the invention it is coated with a third layer, which protects it against air and improves the life of the electronic component (in this case the battery). Advantageously, this third barrier layer is also chosen to withstand a high temperature, and has sufficient mechanical strength to protect it during the subsequent use of the object. Advantageously, the thickness of the third thin covering layer is between 1 μm and 50 μm, preferably less than 10 μm, preferably less than 5 μm and even more preferably around 2 μm.
    This third layer 33 is preferably based on epoxy resin, polyethylene naphthalate (PEN), polyimide, polyamide, polyurethane or silicone. Advantageously, the materials used to make this third layer are chosen to facilitate the assembly of the electronic component. Advantageously, this third layer is deposited by dipping.
    In another embodiment, a pretreatment of the object is carried out before its encapsulation by the encapsulation system according to the invention. This pretreatment of the object consists in covering the object with a layer of parylene, preferably parylene N in order to improve the protection of the object. Preferably, the thickness of parylene is between 1 μm and 50 μm, preferably is approximately 10 μm.
    Primary overlay of anode sheets and cathode sheets / stack of anode and cathode
    Advantageously, the object protected by the encapsulation system according to the invention is a battery and preferably an entirely solid battery.
    In the present description, the term "entirely solid" battery (also called here "all solid") means a battery comprising at least one thin layer of cathode, one thin layer of anode and one thin layer of solid electrolyte, each thin layers with a very small number of pores.
    In the present application, an elementary cell of an entirely solid battery alternately comprises an anode and a cathode, each optionally made up of a stack of thin layers. The anode comprises at least one thin layer of an active anode material and optionally a thin layer of an electrolyte material. The cathode comprises at least a thin layer of an active cathode material and optionally a thin layer of an electrolyte material so that the elementary cell of an entirely solid battery successively comprises at least one thin layer of a material active anode, at least one thin layer of an electrolyte material and at least one thin layer of an active cathode material.
    When the battery is obtained from an alternating succession of at least one anode and at least one cathode, the anode advantageously comprises, successively:
    optionally a thin layer of an electrolyte material, a thin layer of an anode active material, a thin metal layer, a thin layer of an anode active material, and optionally a thin layer of an electrolyte material.
    In the present application, the term “anode sheet” will be used to designate this succession of layers which can be used to produce a primary superposition from which at least one unitary battery will be obtained subsequently, preferably several unitary batteries.
    Likewise, the cathode advantageously and successively comprises:
    optionally a thin layer of an electrolyte material, a thin layer of an active cathode material, a thin metal layer, a thin layer of an active cathode material, and optionally a thin layer of a cathode material electrolyte, so that an entirely solid battery successively comprises at least one thin layer of an active anode material, at least one thin layer of electrolyte material and at least one thin layer of active material cathode.
    In the context of the present invention, the thickness of each of the thin layers present in the battery is less than 10 μm and preferably less than 5 μm.
    In the present application, the term “cathode sheet” will be used to designate this succession of layers which can be used to produce a primary superposition. The primary superposition comprises an alternating succession of cathode sheets and anode sheets, from which at least one unitary battery comprising a stack of at least one anode and at least one cathode will be obtained subsequently, preferably several unit batteries. Two adjacent sheets of this primary superimposition define at least one projecting region, intended to form an accessible connection area, as well as at least one recessed region, intended to form an overlapping area, .i.e. area covered by the encapsulation system. These projecting and recessed regions will be explained in greater detail with regard to two embodiments, which do not limit the invention.
    The present invention relates in particular to the encapsulation of fully solid Li-ion batteries. The entirely solid batteries 1 have a rigid monobloc structure on which an encapsulation system 30 can be deposited (cf. FIG. 1). Figure 3, like Figure 2, is a perspective view with cutaway of an entirely solid battery 1. It shows the internal structure of the central element comprising an assembly of elementary cells 2 covered by an encapsulation system 30 according to the invention and that of the terminations 40. FIG. 4 shows in greater detail an entirely solid battery comprising an anode 10 and a cathode 20, each consisting of a stack of thin layers. The anode successively comprises a thin layer of an electrolyte material 13, a thin layer of an active anode material 12 such as Li 4 Ti 5 0i 2 , a thin metallic layer 11 (for example made of stainless steel) , a thin layer of an anode active material such as Li 4 Ti 5 0i 2 12 and a thin layer of an electrolyte material 13.
    The cathode 20 successively comprises a thin layer of an electrolyte material 23, a thin layer of an active cathode material 22 such as LiMn 2 O 4 , a thin metallic layer 21 (for example made of stainless steel), a layer thin of a cathode active material 22 such as LiMn 2 O 4 ) and a thin layer of an electrolyte material 23, it being understood that the battery comprises an alternating succession of at least one anode 10 and at least at least one cathode 20, two adjacent sheets of which define at least one projecting region, intended to form an accessible connection zone and at least one recessed region, intended to form a covering zone, ie zone covered by the encapsulation system.
    This battery consists of an assembly of several elementary cells connected in parallel, is formed from thin films of anode and cathode preferably made from dimensionally stable materials during the charging and discharging stages of the battery.
    Among the active anode materials which can be used to achieve such a function, mention may be made of insertion materials of the Li 4 Ti 5 0i 2 type , certain of the nitrides of the Li 3 type. x M x N in a limited lithium insertion range, as well as other anodes of the Li y SiTON or Sn 3 N 4 type .
    The lithium insertion materials used to make the cathodes are often much more dimensionally stable than the anode materials. Oxides with a spinel structure such as LiMn 2 O 4 , LiMn 1 , 5 Ni 0 , 5O 4 , as well as olivine-type structures such as LiFePO 4 are particularly dimensionally stable, and their use is preferred in the context of the present invention.
    Likewise, these active anode and cathode materials are assembled using solid electrolytes in order to ensure a rigid and stable surface for encapsulation and to avoid the risk of deterioration of the latter during the cycles d use of the battery. These solid electrolytes can be polymers, ceramics, glasses, glass-ceramics and / or hybrid materials composed of both an organic and an inorganic part.
    To provide excellent protection against atmospheric gases, it is necessary to have a protective film which has an extremely low WVTR. According to the state of the art, the best protections are offered by metallic films, however the latter cannot cover the entire battery without shorting the electrodes.
    After the stacking step (cf. FIGS. 4, 7 and 15) and before adding the terminations, the stack is encapsulated in an encapsulation system according to the invention making it possible to protect the screw battery. -to the atmosphere.
    Encapsulation system
    The quality of the encapsulation is of paramount importance for Liion type batteries. The encapsulation system 30 according to the invention is chemically stable, withstands high temperature, offers protection against humidity and is impermeable to the atmosphere to perform its barrier layer function. It consists of several layers deposited successively on the stack (see Figures 5 and 8), as described above.
    To do this, the encapsulation system according to the invention consists of several layers deposited successively on the object, in particular on the parts of the object needing to be protected.
    This encapsulation system allows electrical insulation and sealing of electronic components or batteries while ensuring the possibility of being able to subsequently connect them electrically to each other and / or with external connection points.
    After the step of encapsulating the electronic component, terminations are added to establish the electrical contacts necessary for the proper functioning of said component.
    terminations
    To make the terminations 40, the coated stack is cut along cutting planes making it possible to obtain unitary battery components, with the stripping on each of the cutting planes of the connections (+) and (-) of the battery , especially in the protruding regions. A termination system is placed on and around these connections (see Figure 6). The connections can then be metallized using plasma deposition techniques known to those skilled in the art, preferably by ALD (cf. FIG. 6 or FIG. 10, item 41) and / or by immersion in a conductive epoxy resin ( charged with silver - (see Figure 6 or Figure 10, item 42) and / or a molten tin bath (see Figure 6 or Figure 10, item 43) .The terminations are preferably made of a stack of layers successively comprising a first thin metal covering layer deposited by ALD 41, a second layer of epoxy resin loaded with Ag 42 deposited on the first layer and a third layer based on tin 43 deposited on the second layer.
    The first conductive layer deposited by ALD 41 serves to protect the section of the battery from humidity. This first conductive layer deposited by ALD is optional. It increases the calendar life of the battery by reducing the WVTR at the termination level. The second layer of epoxy resin loaded with Ag 42 makes it possible to provide “flexibility” to the connectors without breaking the electrical contact when the electrical circuit is subjected to thermal and / or vibratory stresses.
    The third layer of tin-based metallization 43 serves to reduce the WVTR, which increases the life of the battery.
    In another embodiment, this third layer can be composed of two layers of different materials. A first layer 43a coming into contact with the layer of epoxy resin loaded with Ag 42. This layer is made of nickel 43a and is produced by electrolytic deposition. The nickel layer acts as a thermal barrier and protects the rest of the component from diffusion during the reflow assembly steps. The last layer 43b, deposited on the nickel layer 43a is also a metallization layer, preferably made of tin to make the interface compatible with reflow assemblies. This tin layer can be deposited either by soaking in a molten tin bath or by electroplating.
    For some assemblies on copper tracks by micro-wiring, it may be necessary to have a last layer 43b of copper metallization. Such a layer can be produced by electrodeposition in place of tin.
    In another embodiment, the terminations can consist of a stack of layers successively comprising a layer of epoxy resin loaded with Ag 42 and a second layer based on tin or nickel 43 deposited on the first layer.
    In another embodiment, the terminations may consist of a stack of layers successively comprising a layer of epoxy resin loaded with Ag 42, a second layer based on nickel 43a deposited on the first layer and a third layer based on d 'tin or copper 43b.
    The terminations allow the alternating positive and negative electrical connections to be taken up at each end of the battery. These terminations allow electrical connections to be made in parallel between the various battery cells. For this, only the connections (+) exit on one end (protruding region), and the (-) are available on the other ends (other protruding regions).
    Description of the process for manufacturing an entirely solid battery according to a first embodiment
    Figure 7 shows according to a first embodiment, like Figure 4, an entirely solid battery comprising anodes 10 and cathodes 20, each consisting of a stack of thin layers; the anodes and the cathodes are offset laterally so as to form projecting regions RS, intended to form an accessible connection area and recessed regions RR, intended to form an overlap area, .i.e. area covered by the encapsulation system.
    In this first embodiment and advantageously, the encapsulation of the battery is carried out on four of the six faces of the stack, it being understood that the cathode sections appearing on a first face and the anode sections appearing on a second face do not are not covered by this encapsulation system so as to facilitate the collection of current on the lateral sides. The encapsulation layers surround the periphery of the stack, the rest of the protection against the atmosphere being provided by the layers obtained by the terminations.
    Preferably, the cathode and anode connections are offset laterally, which allows the encapsulation layer to function as a dielectric to avoid the presence of a short circuit on these ends.
    Once the stack has been made, and after the step of encapsulating the stack, terminations (electrical contacts, cf. FIG. 6, reference 40) are added at the level where the cathode current collectors, respectively anodic current are apparent ( not coated with insulating electrolyte). These contact zones can be on the opposite sides of the stack to collect the current (lateral current collectors) or on adjacent sides (cf. FIG. 9 A and FIG. 9 B).
    Advantageously, the battery according to the invention obtained from a primary superposition, comprising an alternating succession of anode sheets and cathode sheets as indicated above, is characterized in that said encapsulation system completely covers four of the six faces of said battery and partially the two laterally opposite remaining faces, said two remaining faces being partially coated with at least said first covering layer (31.3T) and at least said second layer (32.32 ') and said two remaining faces comprising an anodic connection area and a cathodic connection area. The third covering layer of said encapsulation system hardly penetrates the primary superposition. Consequently, this third layer hardly covers the two remaining laterally opposite faces.
    Description of the process for manufacturing an entirely solid battery according to a second embodiment
    Method for the simultaneous production of several batteries
    First embodiment
    In order to increase the production yield of fully solid batteries, the simultaneous manufacture of several fully solid batteries can be carried out from a primary superposition of alternating sheets comprising between several tens and several hundred anodes delimited along a cutting plane U-shaped and sheets comprising between several tens and several hundred cathodes delimited along a U-shaped cutting plane (cf. FIG. 11, first embodiment). All these sheets have perforations at their four ends so that when these perforations are superposed, all the cathodes and all the anodes of these sheets are superimposed and offset laterally (cf. FIGS. 12 and 13, first embodiment).
    The encapsulation is then carried out as described above according to the arrows (F) present in FIGS. 12 and 13. These arrows indicate the areas covered by the encapsulation system according to the invention (recessed regions).
    The primary superposition of anode sheets and cathode thus coated is then cut by any suitable means so as to expose the anode and cathode current collectors and to obtain unitary batteries.
    Terminations (electrical contacts, see Figure 15, reference 40, 41 ’, 42’ and 43 ’) are added at the level where the cathode current collectors, respectively anodic current are apparent (not coated with insulating electrolyte). These contact areas are preferably arranged on opposite sides of the battery stack to collect current (lateral current collectors) or on adjacent sides.
    Second embodiment
    In another embodiment, the simultaneous manufacture of several entirely solid batteries can be carried out using an alternate primary superposition of sheets comprising between several tens and several hundred anodes 10 ′ having notches 50, 50 ′ and sheets comprising between several tens and several hundred cathodes 20 ′ having notches 50 ”, 50” '. All these sheets have indentations, preferably concentric orifices or holes so that when these perforations are superposed, all the cathodes and all the anodes of these sheets define at least one protruding region RS, intended to form a zone of accessible connection, as well as at least one recessed region RR, intended to form an overlap zone, ie zone covered by the encapsulation system (cf. FIGS. 16, 17, 18 and 19). In FIG. 16, each anode sheet comprises an alternative succession of holes of diameters Dt and D 2 where D 2 is a diameter less than Dt and each cathode sheet comprises an alternative succession of holes of diameters D 2 and Dt where D 2 is a diameter less than so that the holes present on the sheets of anode of diameter Dt (respectively D 2 ) and of cathode of diameter D 2 (respectively DQ are concentric. FIG. 19 shows a similar perspective view in FIG. 16 illustrating on a larger scale the primary superposition of anode sheets and cathode sheets, and in particular the superposition of concentric holes of different diameters Dt and D 2 present on these sheets highlighting the projecting regions and the backward regions.
    The primary superposition of anode sheets and cathode sheets is then covered with the encapsulation system according to the invention comprising:
    - a first covering layer of the encapsulation system 31 ’, identical to the first covering layer of the encapsulation system 31 and deposited on the stack by an atomic layer deposition process,
    - a second encapsulation layer 32 ’comparable to the second encapsulation layer 32 deposited on the first encapsulation layer in order to improve the protection of the battery cells from their external environment,
    - a third layer 33 comparable to the third layer 33 ’deposited on the second encapsulation layer (cf. FIGS. 22 and 23).
    The primary superposition of anode sheets and cathode thus coated is then perforated at the concentric perforations by any appropriate means so that the diameter of these new perforations is between Dt and D 2 and thus lets appear for each hole , either the anode connections or the cathode connections, ie the (+) and (-) connections of the battery (cf. FIGS. 21A and 21 B) in order to facilitate the collection of current in the lateral concentric holes.
    After so-called secondary cutting, in a middle part of said primary superposition, unitary batteries are obtained (cf. FIG. 20) and terminations (electrical contacts, cf. FIG. 24, reference 40, FIG. 27 reference 41 ', 42' and 43 ') are added at the level where the cathodic, respectively anodic current collectors are apparent (not coated with insulating electrolyte). These contact areas are preferably arranged on opposite sides of the battery stack to collect current (lateral current collectors) or on adjacent sides (see Figures 24, 25 to 27).
    The connections are metallized using plasma deposition techniques known to a person skilled in the art, preferably by ALD (cf. FIG. 27, item 41 ') and / or by immersion in a conductive epoxy resin loaded with silver. - (see Figure 27, item 42 ') and / or a molten tin bath (see Figure 27, item 43'). Preferably, the terminations consist of a stack of layers successively comprising a first thin layer of metal covering deposited by ALD 41 ', a second layer of epoxy resin loaded with Ag 42' deposited on the first layer and a third layer based 43 'tin deposited on the second layer. The terminations allow the alternating positive and negative electrical connections to be taken up on each of the concentric ends. These terminations allow electrical connections to be made in parallel between the various battery cells. For this, only the (+) connections exit on a concentric end, and the (-) are available on another concentric end.
    Examples
    The invention is illustrated below by examples which however do not limit the invention. These examples relate to the preparation of an entirely solid battery and the encapsulation of an entirely solid battery.
    1. Preparation of a fully solid Li-ion battery
    A suspension of the anode material at 10 g / l was obtained by grinding then dispersion of Li 4 Ti50i2 in absolute ethanol with the addition of a few ppm of citric acid. A suspension of cathode material at 25 g / l was obtained by grinding and then dispersion of LiMn 2 O 4 in absolute ethanol. The cathode suspension was then diluted in acetone to a concentration of 5 g / l. The suspension of electrolyte material at 5 g / l was obtained by grinding then dispersion of a LisAlo ^ Sc ^ eiPO ^ s powder in absolute ethanol.
    For all these suspensions, the grinding was carried out so as to obtain stable suspensions with a particle size of less than 100 nm.
    The negative electrodes were prepared by electrophoretic deposition of the Li 4 Ti 5 0i 2 nanoparticles contained in the suspension previously prepared. The thin film of Li 4 Ti 5 0i 2 (approximately 1 micron) was deposited on both sides of the substrate. These negative electrodes were then annealed at 600 ° C.
    The positive electrodes were prepared in the same way, by electrophoretic deposition from the suspension of LiMn 2 O 4 . The thin film of LiMn 2 O 4 (approximately μm) was deposited on both sides of the substrate. The positive electrodes were then annealed at 600 ° C.
    After annealing the negative electrodes and the positive electrodes were covered with a Li electrolyte layer 3 AI 0, 4 Sc 16 (PO 4) 3 by EPD. The thickness of Li 3 AI 0, 4 Sc 16 (PO 4) 3 was about 500 nm on each electrode. These electrolyte films were then dried.
    The stacking of anodes and cathodes coated Li 3 Alo, 4Sc 1 , 6 (P04) 3 was then carried out so as to obtain a multilayer stack shifted laterally (cf. FIG. 7). The assembly was then kept under pressure for 15 minutes at 600 ° C to carry out the assembly.
    2. Encapsulation of the entirely solid battery according to the invention
    The encapsulation system was then deposited on the previous multilayer stack. An Al 2 O 3 alumina layer representing the first layer of the encapsulation system was deposited by an atomic layer deposition process (Atomic layer deposition in English, better known by the acronym ALD). The multilayer stack of coated anodes and cathodes was introduced into the chamber of an ALD P300 Picosun reactor. The ALD reactor chamber was previously placed under vacuum at 5 hPa and at 180 ° C. and previously subjected for 30 minutes to a flow of Trimethylaluminium (hereinafter TMA - CAS 75-24-1), a chemical precursor of alumina under nitrogen containing less than 3 ppm type 1 ultrapure water (o ~ 0.05 pS / cm) as carrier gas at a flow rate of 150 sccm (standard cm 3 / min), in order to stabilize the atmosphere of the reactor chamber before any deposition. After stabilization of the chamber, an AI 2 O 3 layer of 100 nm was deposited by ALD.
    CVD then deposited a 12 µm +/- 2 µm thick parylene film N on this first layer of alumina.
    On this second layer was then deposited a third encapsulation layer. This can be carried out on the basis of epoxy resin, polyethylene naphthalate (PEN), silicone, polyimide, polyamide or polyurethane. Preferably, it is made on the basis of an epoxy resin. This third layer was then hardened under ultraviolet (UV) so as to reduce the rate of degradation of the battery by atmospheric elements.
    3. Completion of fully solid battery terminations
    The stack thus encapsulated was then cut along U-shaped cutting planes making it possible to obtain unitary battery components, with the stripping on each of the cutting planes of the cathodic, respectively anodic current collectors of the battery. . The encapsulated stack was thus cut out on two of the six faces of the stack so as to make the cathode current collectors, respectively anodic current collectors, visible. Terminations were then added at the level where the cathode or anode current collectors are apparent (not coated with insulating electrolyte).
    The connections were then metallized by ALD. This first termination layer was then immersed in a conductive epoxy resin (charged with silver) and then immersed in a bath of molten tin.
    The battery thus obtained was cycled between 2 and 2.7 V.
    权利要求:
    Claims (28)
    [1" id="c-fr-0001]
    1. Encapsulation system (30) of an object such as an electronic component or of a battery, characterized in that it is formed by three successive layers comprising (i) a first covering layer (31,3T ) composed of an electrically insulating material deposited by ALD (Atomic Layer Déposition), which at least partially covers said object, (ii) a second covering layer (32,32 ') comprising parylene, placed on the first layer of covering, (iii) a third covering layer (33.33 ′) deposited on the second covering layer so as to protect the second encapsulation layer, in particular from oxygen and to increase the lifetime of the object .
    [2" id="c-fr-0002]
    2. System for encapsulating an object comprising a covering layer comprising parylene, preferably parylene N and an encapsulation system (30) deposited on said covering layer comprising parylene according to claim 1.
    [3" id="c-fr-0003]
    3. Electronic component or battery comprising an encapsulation system (30) according to claim 1 or claim 2.
    [4" id="c-fr-0004]
    4. Battery according to claim 3, comprising an alternating stack between at least one anode (10,10 ') and at least one cathode (20,20'), each consisting of a stack of thin layers and in which the anode (10,10 ') comprises o at least one thin layer of an active anode material (12), and o optionally a thin layer of an electrolyte material (13), and in which the cathode (20 , 20 ') comprises o at least one thin layer of an active cathode material (22), and o optionally a thin layer of an electrolyte material (23) so that the battery successively comprises at least one thin layer an active anode material (12), at least one thin layer of an electrolyte material (13,23) and at least one thin layer of an active cathode material (22), a system for encapsulation (30) according to claim 1, wherein said first layer (31,3Γ) at least partially covers the stack, said system partially covering said stack, a first anode (10) or cathode (20) comprising at least one accessible connection area, while the adjacent cathode (20) or anode (10) comprises a covering area (ZRT), which is covered by at least said first covering layer (31.3T) and said second covering layer (32.32 ′), said covering zone being situated opposite the connection zones (ZC) of the first anode or cathode, in a direction perpendicular to the plane of said stack.
    [5" id="c-fr-0005]
    5. A method of manufacturing an electronic component or an encapsulated battery, comprising the formation of an encapsulation system according to claim 1 and in which one deposits successively so as to form said encapsulation system:
    a first covering layer (31,31 ') composed of an electrically insulating material by ALD (Atomic Layer Déposition), • a second covering layer (32,32') comprising parylene, deposited on said first covering layer, a third covering layer (33,33 ′), deposited on the second covering layer, suitable for and deposited so as to protect the second encapsulation layer, in particular from oxygen.
    [6" id="c-fr-0006]
    6. A method of manufacturing an electronic component or an encapsulated battery, comprising the formation of an encapsulation system according to claim 2 and in which one deposits successively so as to form said encapsulation system:
    a covering layer comprising parylene on said electronic component or said battery a first covering layer (31.3T) composed of an electrically insulating material by ALD (Atomic Layer Deposition) deposited on said covering layer comprising parylene, a second covering layer (32,32 ') comprising parylene, deposited on said first covering layer, "a third covering layer (33,33'), deposited on the second covering layer, suitable for, and deposited so as to , protect the second encapsulation layer, in particular from oxygen.
    [7" id="c-fr-0007]
    7. A method of manufacturing a thin film battery according to claim 5, said battery comprising an alternating stack between at least one anode (10) and at least one cathode (20,20 '), each consisting of a stack of thin layers and in which the anode (10,10 ') comprises:
    o at least one thin layer of an active anode material (12), and o optionally a thin layer of an electrolyte material (13), and in which the cathode (20,20 ’) comprises:
    o at least one thin layer of an active cathode material (22), and o optionally a thin layer of an electrolyte material (23) so that the battery successively comprises at least one thin layer of an active material anode (12), at least one thin layer of an electrolyte material (13,23) and at least one thin layer of an active cathode material (22), said method comprising the following steps:
    (a) a primary superposition is formed, comprising an alternating succession of cathode sheets and anode sheets, said primary superposition being intended to form at least one battery, two adjacent sheets defining at least one projecting region (RS), intended to form said accessible connection zone (ZC), as well as at least one recessed region (RT), intended to form said covering zone (RTC), (b) the encapsulation system according to claim 1 is deposited by the method according to claim 5.
    [8" id="c-fr-0008]
    8. A method of manufacturing a battery according to claim 7 in which, after step (b), the accessible connection area (ZC) or each accessible connection area (ZC) is shown.
    [9" id="c-fr-0009]
    9. A method of manufacturing a battery according to claim 7 or 8 wherein, after step (b), a step (c) is carried out comprising at least one primary cut perpendicular to the plane of said primary superposition so as to render accessible a connection area (ZC) at the level of the anode below anodic connection area and at least one primary cut is made perpendicular to the plane of said primary superposition so as to make a connection area (ZC) accessible of the cathode below cathodic connection area.
    [10" id="c-fr-0010]
    10. A method of manufacturing a battery according to claim 9, characterized in that the primary cuts are made at the opposite edges of said primary superposition.
    [11" id="c-fr-0011]
    11. A method of manufacturing a battery according to any one of claims 7 to
    8, characterized in that the edges of the two adjacent sheets of the primary overlay comprising an alternating succession of cathode sheets and anode sheets are straight edges, the edge of a first sheet forming the projecting region (RS) while the edge of a second sheet forming the recessed region (RR).
    [12" id="c-fr-0012]
    12. A method of manufacturing a battery according to any one of claims 7 to
    9, characterized in that, in the edge of a first sheet of the primary superposition comprising an alternating succession of cathode sheets and anode sheets, first notches (50, 50 ', 50 ”, 50 '”) Having a first or large section, the wall of said first notches constituting said recessed region, and second notches having a second or small section, less than the first section, are produced in a second adjacent sheet, the wall of said second notches (50, 50 ', 50 ”, 50'”) constituting said projecting region (RS).
    [13" id="c-fr-0013]
    13. A method of manufacturing a battery according to claim 12, characterized in that the cathode sheets and the anode sheets have notches (50, 50 ’, 50”, 50 ’”) in the shape of a circle.
    [14" id="c-fr-0014]
    14. A method of manufacturing a battery according to any one of claims 7 to 9, characterized in that one produces, in a first sheet, first orifices having a first or large section, the wall of said orifices constituting said region set back, in a second adjacent sheet, second orifices having a second or small section, smaller than the first section, are produced, the wall of said orifices constituting said projecting region (RS), the interior volume of said orifices is filled by means of the encapsulation system and secondary cuts are made inside said first and second orifices, so that the connection zones (ZC) are formed in the vicinity of the walls having the small section and the overlap zones are formed in the vicinity walls with the large section.
    [15" id="c-fr-0015]
    15. A method of manufacturing a battery according to any one of claims 7 to 11, characterized in that one realizes, in two adjacent sheets, first and second slots, mutually offset in the direction perpendicular to the plane of said sheets, the interior volume of said slots is filled by means of the encapsulation system and secondary cuts are made inside said slots, so that the connection zones are formed in the vicinity of the walls of a first slot and the overlap zones are formed in the vicinity of the walls of a second slot.
    [16" id="c-fr-0016]
    16. A method of manufacturing a battery according to any one of claims 9 to 15 in which, after step (c), the anodic and cathodic connection zones (ZC) are electrically connected to each other by a layer deposition thin of an electronic conductor and in which the deposition is carried out by ALD (41, 4Γ).
    [17" id="c-fr-0017]
    17. A method of manufacturing a battery according to any one of claims 9 to 15 characterized in that one carries out terminations (40, 40 ') anodic and cathodic by metallization of the sections previously covered with a thin layer of an electronic conductor.
    [18" id="c-fr-0018]
    18. A method of manufacturing a battery according to any one of claims 9 to 15 in which, after step (c), the anode and cathode connection zones are electrically connected to each other by a termination system successively comprising:
    o an optional first metal layer, preferably deposited by ALD (41,41 '), o a second layer (42, 42') based on silver-charged epoxy resin, deposited on the first metal layer, and o a third layer (43, 43 ') based on tin, deposited on the second layer.
    [19" id="c-fr-0019]
    19. A method of manufacturing a battery according to any one of claims 9 to 15 in which, after step (c), the anode and cathode connection zones are electrically connected to each other by a termination system successively comprising:
    o a first metallic layer, optional, preferably deposited by ALD (41), o a second layer (42) based on silver-charged epoxy resin, deposited on the first metallic layer, and o a third layer (43a) based on nickel, deposited on the second layer, o a fourth layer (43b) based on tin or copper, deposited on the third layer.
    [20" id="c-fr-0020]
    20. A method of manufacturing a battery according to any one of claims 7 to
    19, in which the sheets have dimensions significantly greater than those of the final battery, characterized in that at least one other so-called secondary cutting is made, in a middle part of said sheets.
    [21" id="c-fr-0021]
    21. A method of manufacturing a battery according to any one of claims 7 to
    20, characterized in that said electrically insulating material is chosen from AI2O3, SiO 2 , SiOyN x , and epoxy resins.
    [22" id="c-fr-0022]
    22. A method of manufacturing a battery according to any one of claims 7 to
    21, characterized in that the second covering layer comprises parylene N.
    [23" id="c-fr-0023]
    23. A method of manufacturing a battery according to any one of claims 7 to
    22, characterized in that the thickness of the first thin covering layer is less than 200 nm, preferably between 5 nm and 200 nm, and even more preferably around 50 nm and the thickness of the second layer overlap is between 1 pm and 50 pm, preferably about 10 pm.
    [24" id="c-fr-0024]
    24. A method of manufacturing a battery according to any one of claims 7 to
    23, characterized in that the thickness of the third thin covering layer is between 1 μm and 50 μm, preferably less than 10 μm, preferably less than 5 μm and even more preferably approximately 2 μm.
    [25" id="c-fr-0025]
    25. A method of manufacturing a battery according to any one of claims 7 to
    24, characterized in that the layer of anode material is produced from a material chosen from:
    - tin oxynitrides (of typical formula SnO x N y );
    - lithiated iron phosphate (of typical formula LiFePO 4 );
    mixed oxynitrides of silicon and tin (of typical formula Si a Sn b O y N z with a> 0, b> 0, a + b ^ 2, 0 <y <4, 0 <z <3) (also called SiTON ), and in particular SiSno, 870i, 2 Ni, 72; as well as the oxynitride-carbides of typical formula Si a Sn b C c O y N z with a> 0, b> 0, a + b <2, 0 <c <10, 0 <y <24, 0 <z <17; If a Sn b C c O y N z Xn with X n at least one of the elements among F, Cl, Br, i, S, Se, Te, P, As, Sb, Bi, Ge,
    Pb and a> 0, b> 0, a + b> 0, a + b <2, 0 <c <10, 0 <y <24 and 0 <z <17; and Si a Sn b O y N z X n with X n at least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb and a> 0, b> 0, a + b <2, 0 <y <4 and 0 <z <3;
    - nitrides of type Si x N y (in particular with x = 3 and y = 4), Sn x N y (in particular with x = 3 and y = 4), Zn x N y (in particular with x = 3 and y = 4), LÎ3_ X M X N (with M = Co and 0 <x <0.5, with M = Ni and 0 <xs0.6 or with M = Cu and 0 <x <0.3);
    - the oxides SnO 2 , Li 4 Ti 5 Oi 2 , SnB0.6P0.4O2.9 and TiO 2 .
    [26" id="c-fr-0026]
    26. Method according to any one of claims 7 to 25, characterized in that the layer of electrolyte material is produced from electrolyte material chosen from:
    o garnets of formula Li d A 1 x A 2 / TO4) Z where A 1 represents a cation of oxidation state + II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and where A 2 represents a cation of oxidation state -Mil, preferably Al, Fe, Cr, Ga, Ti, La; and where (TO 4 ) represents an anion in which T is an atom of degree of oxidation + IV, located at the center of a tetrahedron formed by the oxygen atoms, and in which TO 4 advantageously represents the silicate anion or zirconate, knowing that all or part of the elements T of an oxidation state + IV can be replaced by atoms of an oxidation state + III or + V, such as Al, Fe, As, V, Nb, ln, Ta;
    knowing that: d is between 2 and 10, preferably between 3 and 9, and even more preferably between 4 and 8; x is 3 but can be between 2.6 and 3.4 (preferably between 2.8 and 3.2); y is 2 but can be between 1.7 and 2.3 (preferably between 1.9 and 2.1) and z is 3 but can be between 2.9 and 3.1;
    o garnets, preferably chosen from: Li 7 La 3 Zr 2 O 12 ; Li 6 La 2 BaTa 2 O 12 ; Li 5 , 5La 3 Nbi i 75lno.250i 2 ; Li 5 La3M 2 O 12 with M = Nb or Ta or a mixture of the two compounds; the Li 7 . x Ba x La3. x M 2 O 12 with 0 <x <1 and M = Nb or Ta or a mixture of the two compounds; the Li 7 _ x La3Zr 2 . x M x O 12 with 0 £ x ^ 2 and M = Al, Ga or Ta or a mixture of two or three of these compounds;
    o lithiated phosphates, preferably chosen from: Li 3 PO 4 ; Li 3 (Sc 2 _ x M x ) (PO 4 ) 3 with M = AI or Y and 0 sxs 1; Li 1 + x Mx (Sc) 2 . x (PO 4 ) 3 with M = Al, Y, Ga or a mixture of the three compounds and 0 S xi 0.8; Li 1 + x M x (Gai. y Sc y ) 2 _ x (PO 4 ) 3 with 0 sxs 0.8; 0 <yi 1 and M = Al or Y or a mixture of the two compounds; Lii + x M x (Ga) 2 . x (PO4) 3 with M = Al, Y or a mixture of the two compounds and 0 sx <
    0.8; Li 1 + x Al x Ti z . x (PO 4 ) 3 with 0 <x <1, or Li 1 + x Al x Ge z . x (PO 4 ) 3 with 0 <x <1, or Li 1 + x12 M x (Ge 1 _ y Ti y ) 2 . x If 2 P 3 . 2 O 12 with 0 <x <0.8 and 0 <y <1.0 & 0 <z <0.6 and M = Al, Ga or Y or a mixture of two or three of these compounds; Li 3 + y (Sc2. x M x ) QyP 3 . y O 12 , with M = Al and / or Y and Q = Si and / or Se, 0 £ x <0.8 and 0 <y <1; or Li 1 + x + yM x Sc2. x QyP 3 .yO 1 2, with M = Al, Y, Ga or a mixture of the three compounds and Q = Si and / or Se, 0 sx <0.8 and 0 <y <1; or Li 1 + x + y + 7 M x (Gai_ „Sc y ) 2 . x Q z P 3 ^ Oi 2 with 0 xs 0.8; 0 £ y <1; 0 sz ί 0.6 with M = Al or Y or a mixture of the two compounds and Q = Si and / or Se; or Li 1 + x N x M 2 . x P 3 O 1 2, with 0 5 x £ 1 and N = Cr and / or V, M = Sc, Sn, Zr, Hf, Se or Si, or a mixture of these compounds;
    o the lithium-containing sulfur compounds, preferably chosen from: Li x AI 2 .yGa y S w (P0 4 ) c with 4 <w <20, 3 <x <10, 0Sy <1, 1 ^ z <4 and 0 <c <20; the Li x AI 2 . y Ga y S w (BO 3 ) c with 4 <w <20, 3 <x <10, 0Îy <1, 1i = z <4 and 0 <c <20; Li x Al z . y SCyS w (PO 4 ) c with 4 <w <20, 3 <x <10, 0i = y <1, 1 ^ z <4 and 0 <c <20; LixAlz-yScyS ^ BO ^ c with 4 <w <20, 3 <x <10, 0 ^ y <1, 1üz <4 and 0 <c <20; Li x Ge z _ y Si y S w (PO 4 ) c with 4 <w <20, 3 <x <10, 0ëy <1, 1 ^ z <4 and 0 <c <20; Li x Ge ( Z. y ) If y S w (BO 3 ) c with 4 <w <20, 3 <x <10, 0 ^ y <1.1 ^ z <4 and 0 <c <20;
    o the lithiated borates, preferably chosen from: Li 3 (Sc2. x M x ) (BO 3 ) 3 with M = AI or Y and 0 sxs 1; Li 1 + x M x (Sc) 2 -x (BO 3 ) 3 with M = Al, Y, Ga or a mixture of the three compounds and 0 ê x <0.8; 0 sy ê 1; Li 1 + x M x (Gai. y Sc y ) 2- x (BO 3 ) 3 with 0 <x <0.8; 0 £ ys 1 and M = Al or Y; Li 1 + x M x (Ga) 2.x (BO 3 ) 3 with M = Al, Y or a mixture of the two compounds and 0 £ x £ 0.8; 0 sy £ 1; Li 3 BO 3r Li 3 BO 3 -Li2SO 4 , Li 3 BO 3 -Li 2 SiO 4 , Li 3 BO 3 -Li2SiO 4 -LÎ2SO 4 ;
    o oxynitrides, preferably chosen from LisPO ^ N ^, Li 4 SiO 4 . x N2 ) 03 , Li 4 GeO 4 . x N 2x / 3 with 0 <x <4 or Li 3 BO3- x N 2x / 3 with 0 <x <3; materials based on lithium oxynitrides of phosphorus or boron (called LiPON and L1BON) which may also contain silicon, sulfur, zirconium, aluminum, or a combination of aluminum, boron, sulfur and / or silicon, and boron for lithium phosphorus oxynitrides;
    o the lithiated oxides, preferably chosen from Li 7 La 3 Zr 2 Oi2 or Li 5 + x La 3 (Zr x , A z . x ) Oi2 with A = Sc, Y, Al, Ga and 1,4 < x <2 or Li 0, 3 5Lao, 55Ti0 3;
    o silicates, preferably chosen from Li2Si 2 O 51 Li 2 SiO 3 , Li2Si 2 O 6 , LiAISiO 4 , Li 4 SiO 4 , LiAISi 2 O6;
    o solid electrolytes of anti-perovskite type chosen from:
    Li 3 OA with A a halide or a mixture of halides and preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these elements;
    Li (3. X ) M x ^ OA with 0 <x <3, M a divalent metal, preferably at least one of the elements chosen from Mg, Ca, Ba, Sr or a mixture of two or three or four of these elements , A halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these elements;
    Lio-xjNxeOA with 0 <x <3, N a trivalent metal, A a halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these elements;
    LiCOX z Y (i. Z) , with X and Y halides and 0 <z <1;
    o electrolytes based on polymers conducting lithium ions impregnated or not with lithium salts, o hybrid electrolytes comprising an inorganic matrix such as a ceramic matrix in which an organic electrolyte comprising lithium salts is inserted.
    [27" id="c-fr-0027]
    27. Thin film battery capable of being obtained by the method according to any one of claims 7 to 26.
    [28" id="c-fr-0028]
    28. Thin film battery capable of being obtained by the method according to any one of claims 9 to 26, characterized in that said encapsulation system completely covers four of the six faces of said battery and partially the two remaining sides laterally opposite, said two remaining faces being partially coated with at least said first covering layer (31.31 ') and at least said second layer (32.32') and said two remaining faces comprising an anodic connection zone and a cathodic connection area.
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    同族专利:
    公开号 | 公开日
    FR3068830B1|2019-08-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5561004A|1994-02-25|1996-10-01|Bates; John B.|Packaging material for thin film lithium batteries|
    US20020071989A1|2000-12-08|2002-06-13|Verma Surrenda K.|Packaging systems and methods for thin film solid state batteries|
    EP2868770A1|2013-10-29|2015-05-06|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Device for encapsulating a sensitive device and method for manufacturing said device|
    CN105552254A|2016-03-02|2016-05-04|郭菲|Corrosion-prevention and compression-resistant lithium battery shell and production method therefor|WO2020249877A1|2019-06-13|2020-12-17|I-Ten|Lithium-ion battery and method for the manufacture thereof|
    FR3105602A1|2019-12-24|2021-06-25|I-Ten|Battery-type electrochemical device, comprising advanced sealing means, and its manufacturing process|
    WO2021130697A1|2019-12-24|2021-07-01|I-Ten|Method for producing lithium-ion batteries, in particular high power lithium-ion batteries, and battery obtained by this method|
    法律状态:
    2018-07-30| PLFP| Fee payment|Year of fee payment: 2 |
    2019-01-11| PLSC| Publication of the preliminary search report|Effective date: 20190111 |
    2019-07-31| PLFP| Fee payment|Year of fee payment: 3 |
    2020-07-27| PLFP| Fee payment|Year of fee payment: 4 |
    2021-07-26| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1756364|2017-07-06|
    FR1756364A|FR3068830B1|2017-07-06|2017-07-06|ENCAPSULATION SYSTEM FOR ELECTRONIC COMPONENTS AND BATTERIES|FR1756364A| FR3068830B1|2017-07-06|2017-07-06|ENCAPSULATION SYSTEM FOR ELECTRONIC COMPONENTS AND BATTERIES|
    PCT/FR2018/051582| WO2019002768A1|2017-06-29|2018-06-28|Encapsulation system for electronic components and batteries|
    EP18752541.5A| EP3646398B1|2017-06-29|2018-06-28|Encapsulation system for electronic components and batteries|
    EP20189732.9A| EP3840110A1|2017-06-29|2018-06-28|Encapsulation system for electronic components and batteries|
    JP2019571597A| JP2020527825A|2017-06-29|2018-06-28|Sealing system for electronic components and batteries|
    SG11201911689QA| SG11201911689QA|2017-06-29|2018-06-28|Encapsulation system for electronic components and batteries|
    US16/625,866| US20200152925A1|2017-06-29|2018-06-28|Encapsulation system for electronic components and batteries|
    CA3065287A| CA3065287A1|2017-06-29|2018-06-28|Encapsulation system for electronic components and batteries|
    CN201880044052.5A| CN110809830A|2017-06-29|2018-06-28|Packaging system for electronic components and batteries|
    IL271156A| IL271156D0|2017-06-29|2019-12-03|Encapsulation system for electronic components and batteries|
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