Encapsulation system for electronic components and batteries

Abstract

Systems, methods, and apparatus for encapsulating objects like that of microelectronic components and batteries. The system includes three successive layers that include a first covering layer composed of an electrically insulating material deposited by atomic layer deposition, which at least partly covers the object, a second covering layer that includes parylene and/or polyimide, and which is disposed on the first covering layer, and a third covering layer deposited on the second covering layer in such a way as to protect the second encapsulation layer, namely, with respect to oxygen, and thereby increase the service life of the object.

Claims

1. A system for encapsulating a battery, the system comprising: a plurality of covering layers that include: a first covering layer composed of an electrically insulating material deposited by atomic layer deposition, which at least partly covers said battery, a second covering layer disposed on the first covering layer, and a third covering layer disposed on the second covering layer to protect the second covering layer with respect to oxygen, wherein: said battery comprises a stack alternating between at least one anode and at least one cathode, that respectively include a stack of thin films, the at least one anode includes at least one thin film of an active anode material, or at least one thin film of an active anode material and a thin film of an electrolyte material, the at least one cathode includes at least one thin film of an active cathode material, or at least one thin film of an active anode material and a thin film of an electrolyte material such that the battery successively has at least one thin film of an active anode material, at least one thin film of an electrolyte material, and at least one thin film of an active cathode material, the at least one anode has at least one anode connection zone or the at least one cathode has at least one cathode connection zone, and an adjacent at least one cathode or an adjacent at least one anode having a covering zone which is covered by at least the first covering layer and the second covering layer, and the covering zone is located facing the at least one anode connection zone or the at least one cathode connection zone in a direction perpendicular to a plane of the stack.

2. The system of claim 1, wherein the second covering layer comprises parylene and/or polyimide.

3. The system of claim 1, wherein said electrically insulating material is selected from the group consisting of Al.sub.2O.sub.3, SiO.sub.2, SiO.sub.yN.sub.x, and epoxy resins.

4. The system of claim 1, wherein the second covering layer comprises parylene N.

5. The system of claim 1, wherein the thickness of: the first covering layer is less than 200 nm, the second covering layer is between 1 μm and 50 μm, and the third covering layer is between 1 μm and 50 μm.

6. The system of claim 1, further comprising a fourth covering layer comprising parylene and/or polyimide formed on the battery, and wherein the first covering layer is disposed on the fourth covering layer.

7. The system of claim 1, wherein: the at least one anode connection zone is covered with a thin film of an electronic conductor to establish an electrical connection to other anode connection zones in the at least one anode connection zone, and the at least one cathode connection zone is covered with a thin film of an electronic conductor to establish an electrical connection to other cathode connection zones in the at least one cathode connection zone.

8. The system of claim 7, wherein: the at least one anode connection zone is metallized, and the at least one cathode connection zone is metallized.

9. The system of claim 8, wherein the at least one anode connection zone and the at least one cathode connection zone are electrically connected to each other by an interconnection system successively comprising: a first electrically conductive layer on the at least one anode connection zone and the at least one cathode connection zone, a second layer, containing epoxy resin impregnated with silver, on the first electrically conductive layer or on the at least one anode connection zone and the at least one cathode connection zone, and a third layer, containing tin, on the second layer.

10. The system of claim 8, wherein the at least one anode connection zone and the at least one cathode connection zone are electrically connected to each other by an interconnection system successively comprising: a first electrically conductive layer on the at least one anode connection zone and the at least one cathode connection zone, a second layer, containing epoxy resin impregnated with silver, on the first electrically conductive layer or on the at least one anode connection zone and the at least one cathode connection zone, a third layer, containing nickel, on the second layer, and a fourth layer, containing tin or copper, on the third layer.

11. The system of claim 8, wherein: the battery has six faces, the encapsulation system totally coats four faces of the six faces and partially coats two laterally opposite remaining faces, two remaining faces comprise an anode connection zone and a cathode connection zone, and the two remaining faces are partially coated by at least the first covering layer and at least the second layer.

12. A battery, comprising: at least one anode including at least one thin film of an active anode material, or at least one thin film of an active anode material and a thin film of an electrolyte material; at least one cathode including at least one thin film of an active cathode material, or at least one thin film of an active anode material and a thin film of an electrolyte material so that the battery successively includes at least one thin film of the active anode material, at least one thin film of the electrolyte material, and at least one thin film of the active cathode material; a primary superposition of a stack of thin films alternating between the at least one anode and the at least one cathode; and an encapsulation system for the battery, the encapsulation system having a plurality of covering layers that include: a first covering layer at least partially covering the stack, the first covering layer composed of an electrically insulating material, a second covering layer composed of parylene and/or polyimide, disposed on the first covering layer, and a third covering layer disposed on the second covering layer in such a way as to protect the second covering layer from exposure to oxygen, and thereby increase the service life of the electronic component or the electrochemical component, wherein: the at least one anode or the at least one cathode includes at least one accessible connection zone, and at least one adjacent cathode or at least one adjacent anode includes a covering zone which is covered by at least the first covering layer and the second covering layer, the covering zone being located facing the connection zones of the at least one first anode or the at least one cathode, in a direction perpendicular to a plane of the stack.

13. The battery of claim 12, wherein: the at least one anode connection zone is covered with a thin film of an electronic conductor to establish an electrical connection to other anode connection zones in the at least one anode connection zone, and the at least one cathode connection zone is covered with a thin film of an electronic conductor to establish an electrical connection to other cathode connection zones in the at least one cathode connection zone.

14. The battery of claim 12, wherein: the at least one anode connection zone is metallized, and the at least one cathode connection zone is metallized.

15. The battery of claim 12, wherein the at least one anode connection zone and the at least one cathode connection zone are electrically connected to each other by an interconnection system successively comprising: a first electrically conductive layer on the at least one anode connection zone and the at least one cathode connection zone, a second layer, containing epoxy resin impregnated with silver, on the first electrically conductive layer or on the at least one anode connection zone and the at least one cathode connection zone, and a third layer, containing tin, on the second layer.

16. The battery of claim 12, wherein the at least one anode connection zone and the at least one cathode connection zone are electrically connected to each other by an interconnection system successively comprising: a first electrically conductive layer on the at least one anode connection zone and the at least one cathode connection zone, a second layer, containing epoxy resin impregnated with silver, on the first electrically conductive layer or on the at least one anode connection zone and the at least one cathode connection zone, a third layer, containing nickel, on the second layer, and a fourth layer, containing tin or copper, on the third layer.

17. A system, comprising: an electronic component or an electrochemical component that includes a primary superposition of a stack of thin films alternating between at least one anode and at least one cathode, the at least one anode including at least one thin film of an active anode material or at least one thin film of an active anode material and a thin film of an electrolyte material, and the at least one cathode including at least one thin film of an active cathode material or at least one thin film of an active anode material and a thin film of an electrolyte material so that the electronic component or the electrochemical component successively includes at least one thin film of the active anode material, at least one thin film of the electrolyte material, and at least one thin film of the active cathode material; an encapsulation system for the electronic component or an electrochemical component, the encapsulation system having a plurality of covering layers that include: a first covering layer at least partially covering the stack, the first covering layer being composed of an electrically insulating material, a second covering layer composed of parylene and/or polyimide, disposed on the first covering layer, and a third covering layer disposed on the second covering layer to protect the second covering layer from exposure to oxygen, wherein: the at least one anode or the at least one cathode includes at least one accessible connection zone, and at least one adjacent cathode or at least one adjacent anode includes a covering zone which is covered by at least the first covering layer and the second covering layer, the covering zone being located facing the connection zones of the at least one first anode or the at least one cathode, in a direction perpendicular to a plane of the stack.

Description

DRAWINGS

(1) FIGS. 1 to 27 illustrate certain aspects of the invention, but do not limit its scope.

(2) FIG. 1 schematically shows, a battery that reveals a central element and interconnections disposed at the two ends of the central element.

(3) FIG. 2 shows a perspective view with a cut along the line II-II of an entirely solid battery, revealing the inner structure of the central element comprising an assembly of elementary cells covered by an encapsulation system according to the invention and that of the interconnections.

(4) FIG. 3 is a perspective view with a cut analogous to FIG. 2 illustrating on a greater scale the detail III of this FIG. 2. The elements forming the elementary cells, the encapsulation system and the interconnections are presented in greater detail in FIGS. 4, 5 and 6, respectively.

(5) FIG. 4 is a perspective view with a cut analogous to FIG. 3 illustrating on a greater scale the detail IV of this FIG. 3, illustrating the inner structure of various elements forming an all-solid battery.

(6) FIG. 5 is a perspective view with a cut analogous to FIG. 4 illustrating on a greater scale the inner structure of the encapsulation system according to the invention.

(7) FIG. 6 is a perspective view with a cut analogous to FIG. 4 illustrating on a greater scale the inner structure of the interconnections.

(8) FIG. 7 shows an exploded perspective view of the stack of the anode and cathode thin films, in such a way that these layers are offset laterally.

(9) FIG. 8 shows an exploded perspective view of the system for encapsulating according to the invention the stack of the anode and cathode layers comprising a stack of covering layers.

(10) FIG. 9A shows a view at the outlet of the anode showing the anode current collectors surrounded on their periphery by the encapsulation system. FIG. 9B shows a view at the outlet of the cathode showing the cathode current collectors surrounded on their periphery by the encapsulation system.

(11) FIG. 10 shows an exploded perspective view of the interconnections of an all-solid battery, consisting of a stack of layers.

(12) FIG. 11 schematically shows the method for manufacturing a plurality of all-solid batteries from an alternating stack of sheets comprising between several tens of and several hundred anodes defined according to a cutting plane in the shape of a U and of sheets comprising between several tens of and several hundred cathodes defined according to a cutting plane in the shape of a U.

(13) FIG. 12 shows a perspective view with a cut of an all-solid battery, along the line XII-XII of FIG. 11 showing the stack of the sheets of anodes and of cathodes superimposed and offset laterally.

(14) FIG. 13 shows a perspective view with a cut of an all-solid battery, along the line XIII-XIII of FIG. 11 showing the stack of the sheets of anodes and of cathodes superimposed and offset laterally.

(15) FIG. 14 shows a perspective view with a cut of an all-solid battery showing the stack of the sheets of anodes and of cathodes superimposed and offset laterally, as well as the encapsulation system and the interconnections.

(16) FIG. 15 shows a perspective view with a cut analogous to FIG. 14 illustrating on a greater scale the detail VI of this FIG. 14, illustrating the inner structure of various elements forming an all-solid battery.

(17) FIG. 16 schematically shows, according to another embodiment, the method for manufacturing a plurality of all-solid batteries.

(18) FIG. 17 schematically shows a cross-sectional view illustrating on a greater scale the detail VII of FIG. 16.

(19) FIG. 18 shows a perspective view analogous to FIG. 16 illustrating on a greater scale the detail VIII of this FIG. 16.

(20) FIG. 19A shows a perspective view with a cut of an all-solid battery, along the line XIX-XIX of FIG. 18. FIG. 19B shows a perspective view with a cut of an all-solid battery, along the line XIX′-XIX′ of FIG. 18.

(21) FIG. 20 shows a perspective view of the structure presented in FIG. 18 covered with the encapsulation system.

(22) FIG. 21A shows a perspective view with a cut of an all-solid battery, along the line XXI-XXI of FIG. 20. FIG. 21B shows a perspective view with a cut of an all-solid battery, along the line XXI′-XXI′ of FIG. 20.

(23) FIG. 22 shows a perspective view analogous to FIG. 21A illustrating on a greater scale the detail IX of this FIG. 21A.

(24) FIG. 23 shows a perspective view analogous to FIG. 22 illustrating on a greater scale the detail X of this FIG. 22.

(25) FIG. 24 shows 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 the interconnections.

(26) FIG. 25A shows a perspective view with a cut of an all-solid battery, along the line XXV-XXV or XXV′-XXV′ of FIG. 24 showing the stack of the superimposed sheets of anodes having anode contacts covered laterally by the multilayer system of the interconnections.

(27) FIG. 25B shows a perspective view with a cut of an all-solid battery, along the line XXV-XXV or XXV′-XXV′ of FIG. 24 showing the stack of the superimposed sheets of cathodes having cathode contacts covered laterally by the multilayer system of the interconnections.

(28) FIG. 26 shows a perspective view analogous to FIG. 25 illustrating on a greater scale the detail XI of this FIG. 25.

(29) FIG. 27 shows a perspective view analogous to FIG. 26 illustrating on a greater scale the detail XII of this FIG. 26.

(30) FIGS. 28a and 28b show a cross-sectional view of a portion of the object 1000 such as an electronic or electrochemical component covered by the encapsulation system according to the invention.

(31) FIGS. 29a and 29b show a cross-sectional view of a portion of the object 1000 such as an electronic or electrochemical component covered by the encapsulation system according to the first alternative of the invention.

(32) FIGS. 30a and 30b show a cross-sectional view of a portion of the object 1000 such as an electronic or electrochemical component covered by the encapsulation system according to the second alternative of the invention.

(33) FIGS. 31a and 31b show a cross-sectional view of a portion of the object 1000 such as an electronic or electrochemical component covered by the encapsulation system according to the third alternative of the invention.

(34) FIG. 32 is a diagram of a method for manufacturing a system for encapsulating an object 1000 according to the invention.

(35) FIG. 33 is a diagram of a method for manufacturing a battery encapsulated by the encapsulation system according to the invention.

DESCRIPTION

(36) The present invention relates to a system for encapsulating an object 1000 providing it with electrical insulation and protecting it from the outside environment, and namely from the ambient atmosphere. The encapsulation system according to the invention allows to offer a protection adapted to the stresses that the electronic components must effectively be able to withstand without notable disturbance of their operation or without damage.

(37) The system for encapsulating an object according to the invention, shown in FIG. 28a, comprises:

(38) i. a first covering layer composed of an electrically insulating material deposited by ALD (Atomic Layer Deposition) intended to at least partly cover said object,

(39) ii. a second covering layer comprising parylene and/or polyimide disposed on the first covering layer,

(40) iii. a third covering layer deposited on the second covering layer in such a way as to protect the second layer of the encapsulation system, namely from oxygen and to increase the service life of the object.

(41) The encapsulated object can be a component that is electronic (such as an integrated circuit, a resistor, a capacitor), or electrochemical such as a battery, a photovoltaic panel.

(42) The first covering layer 31 of the encapsulation system consists of an electrically insulating material such as Al2O3, SiO2, SiOyNx and the epoxy resins. Advantageously, said electrically insulating material is chosen from organic or inorganic polymer materials having barrier properties with regard to water. This first layer is deposited on at least a portion of said object by a conformal deposition technique, such as an atomic layer deposition method (Atomic Layer Deposition, better known by the acronym ALD). When the object is a battery, the first covering layer 31 is deposited on the stack or the primary superposition by ALD. Thus a conformal covering of all of the accessible surfaces of the stack is obtained; this first layer is preferably an inorganic layer.

(43) The techniques of deposition by ALD are particularly well adapted to covering surfaces having a high roughness in a totally impermeable and conformal manner. The techniques of deposition by ALD allow to make conformal layers, free of defects, of holes. These layers are qualified as “free of holes” (pinhole free) and represent very good barriers. Their WVTR coefficient is extremely low. The WVTR (Water Vapor Transmission Rate) coefficient allows to evaluate the permeance to water vapor of the encapsulation system. The lower the WVTR coefficient, the more impermeable the encapsulation system. For example, a deposit of Al2O3 100 nm thick by ALD has a permeation to water vapor of 0.00034 g/m2.d.

(44) The first encapsulation layer thus obtained can be made of ceramic material, made of glass material or made of glass-ceramic material. It generally consists of oxides, of the type Al2O3, of nitride, of phosphates, of oxynitride, of siloxane, having a thickness of less than 200 nm, preferably between 5 nm and 200 nm, more preferably between 10 nm and 100 nm and even more preferably approximately fifty nanometers. However, these layers deposited by ALD are very mechanically fragile and require a rigid bearing surface. The deposition of a fragile layer on a flexible surface would lead to the formation of cracks, engendering a loss of integrity of this protective layer. Moreover, in order to industrially allow a relatively high rate of deposition, these layers must be deposited at a rather high temperature, i.e. at a temperature between 180° C. and 300° C. The materials forming the object must thus resist such temperatures and have a surface sufficiently rigid to guarantee the creation of a quality encapsulation by ALD. This applies in particular to the rigid stacks, to the one-piece solid stacks of lithium-ion cells, i.e. of lithium-ion battery. However, most of the usual electrolytes containing polymers containing lithium salts, i.e. electrolytes in the form of a gel, liquid or containing pockets of liquid, do not resist such a temperature and do not have a surface sufficiently rigid to guarantee the creation of a reliable encapsulation by ALD. Indeed, under vacuum and at a high temperature, these electrolytes degas and thus prevent the creation of homogenous and protective thin deposits directly on their surfaces. Preferably, the use of these electrolytes in batteries that will use the encapsulation system according to the invention will therefore be avoided.

(45) An exception can be made for the lithium-ion batteries using at least one porous electrode and/or at least one electrolyte comprising a porous inorganic layer, the electrode and the porous inorganic layer having an interconnected network of open pores in which the average diameter D50 of the pores is between 2 nm and 80 nm, preferably between 2 nm and 50 nm, preferably between 6 nm and 30 nm, and even more preferably between 8 nm and 20 nm and the pores of which, because of their size, are capable of absorbing a liquid phase by simple capillarity and are impregnated with a phase carrying lithium ions, i.e. by an electrolyte, such as a solution formed by a lithium salt dissolved in an organic solvent or a mixture of organic solvents, and/or comprising a polymer containing at least one lithium salt possibly dissolved in an organic solvent or a mixture of organic solvents, and/or comprising at least one ionic liquid containing at least one lithium salt possibly dissolved in an organic solvent or a mixture of organic solvents.

(46) The liquid phase “nanoconfined” or “nanotrapped” in the porosities, preferably in the mesoporosities, can no longer come out again. It is bound by a phenomenon called here “absorption in the mesoporous structure” (which does not appear to have been described in the literature in the context of lithium-ion batteries) and can no longer come out even when the cell is placed under vacuum. This battery comprising such a porous electrode and/or such an electrolyte is thus considered to be quasi-solid. Via the nanoconfinement of the conductive phase carrying lithium ions in the porosities, the battery can undergo treatments under vacuum contrary to the lithium-ion batteries that use separators impregnated with usual electrolytes as indicated above; these lithium-ion batteries using separators are not sufficiently rigid to undergo these treatments under vacuum without being degraded.

(47) When the object 1000 is a battery, this first encapsulation layer 31 also allows 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 closer together of the electrodes.

(48) 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 or electrochemical component such as a battery) from its outside environment. Typically, this second layer is made of polymer, for example made of silicone (deposited for example by impregnation or by plasma-assisted chemical vapor deposition using hexamethyldisiloxane (HMDSO)), or made of epoxy resin, or made of polyimide, or made of parylene, preferably made of parylene and/or made of polyimide. This second encapsulation layer is advantageously obtained from the condensation of gaseous monomers deposited by chemical vapor deposition (CVD) on the surfaces, which allows to have a conformal and uniform covering of all of the surfaces of the accessible object.

(49) This second layer ensures the filling of the encapsulation system without degrading the first layer of the encapsulation system. It allows to follow the variations in volume of the object during its operation and facilitates the cutting itself of the batteries via its elastic properties. The thickness of said second encapsulation layer is between 1 μm and 50 μm, preferably between 1 μm and 35 μm, preferably between 2 μm and 10 μm, preferably between 2 μm and 5 μm and even more preferably approximately 3 μm.

(50) Advantageously, on the first covering layer 31, a parylene film is deposited, such as a film of parylene C, of parylene D, a film of parylene N (CAS 1633-22-3) or a film comprising a mixture of parylene C, D, and/or N. This film of parylene allows to protect the sensitive elements of the object from their environment. Parylene (also called polyparaxylylene or poly(p-xylylene)) is a dielectric, transparent, semi-crystalline material that has high thermodynamic stability, excellent resistance to solvents and a very low permeability. Parylene also has barrier properties allowing to protect the object from its outside environment. The protection of the battery is increased when this second encapsulation layer is made from parylene N.

(51) Alternatively, a layer containing polyimide is deposited on the first covering layer. This layer of polyimide protects the sensitive elements of the battery from their environment.

(52) In an alternative and particularly advantageous manner, the second encapsulation layer 32 (i.e. second covering layer) consists of a first layer of polyimide 32′″ deposited on the first covering layer, preferably approximately 1 μm thick on which a second layer of parylene 32″″ is deposited, preferably approximately 2 μm thick. This protection is increased when this second layer of parylene, preferably approximately 2 μm thick is made from parylene N. The layer of polyimide associated with the layer of parylene improves the protection of the sensitive elements of the battery from their environment (cf. FIG. 28b). However, the inventors have observed that this second covering layer deposited on the first encapsulation layer, namely when it is made from parylene, does not have sufficient stability in the presence of oxygen. When this second layer is made from polyimide, it does not have sufficient impermeability, namely in the presence of water. According to the invention, it is coated with a third layer, which protects it from the air and improves the service life of the electronic or electrochemical component (in this case of the battery).

(53) Advantageously, this third barrier layer 33 is also chosen in order to resist a high temperature, and has a mechanical strength sufficient to protect it during the later use of the object. Advantageously, the thickness of the third covering thin film is between 1 μm and 50 μm. Ideally, the thickness of the third covering thin film is approximately 10-15 μm, such a range of thickness allows to protect the battery against mechanical damage. The thickness of the third thin film can be, preferably, less than 10 μm, preferably less than 5 μm and even more preferably approximately 2 μm.

(54) This third layer 33 preferably contains epoxy resin, polyethylene naphthalate (PEN), polyimide, polyamide, polyurethane or silicone. Advantageously the materials used to make this third layer are chosen in order to facilitate the assembly of the electronic or electrochemical component. Advantageously, this third layer is deposited via dipping.

(55) Below, three alternatives of the encapsulation system according to the invention will be described. Then, two embodiments, each of which can be combined with the invention or with any one of the three alternatives of the invention, will be described.

(56) First Alternative of the Invention

(57) According to an advantageous alternative of the invention that is implemented indifferently with one or the other of the embodiments described below, a pretreatment of the object is carried out before its encapsulation by the encapsulation system according to the invention (cf. FIG. 29a). This pretreatment of the object 1000 involves covering it with a polymer layer, preferably containing polyimide and/or parylene, preferably parylene, namely parylene N in order to improve the protection of the object. This pretreatment layer 50 is a covering layer. This pretreatment layer 50 is advantageously used to protect lithium-ion batteries using at least one porous electrode and/or at least one electrolyte comprising a porous inorganic layer as indicated above and where the electrode and the porous inorganic layer have an interconnected network of open pores in which the average diameter D50 of the pores is between 2 nm and 80 nm, preferably between 2 nm and 50 nm, preferably between 6 nm and 30 nm, and even more preferably between 8 nm and 20 nm and the pores of which are impregnated with a phase carrying lithium ions, preferably by an ionic liquid “nanoconfined” or “nanotrapped” in the porosities. This pretreatment layer 50 on this type of lithium-ion battery prevents the possible degassing of the electrolytes during any manipulation of said battery, namely under vacuum and at high temperature.

(58) This pretreatment layer 50 allows to carry out high-performance encapsulations on lithium-ion batteries using at least one porous electrode and/or at least one electrolyte comprising a porous inorganic layer as indicated above, preferably impregnated by a “nanoconfined” ionic liquid.

(59) It can be deposited under vacuum, by a technique of chemical vapor deposition (CVD). This pretreatment layer 50 is advantageously obtained using the condensation of gaseous monomers deposited by a technique of chemical vapor deposition (CVD) on the surfaces, which allows to have a conformal and uniform covering of all of the accessible surfaces of the stack. It allows to follow the variations in volume of the object such as a battery during its operation and facilitates the cutting itself of the batteries via its elastic properties. Preferably, the thickness of this pretreatment layer is between 1 μm and 50 μm, preferably between 2 μm and 10 μm, preferably between 2 μm and 5 μm and even more preferably approximately 3 μm. It allows to cover all of the accessible surfaces of the stack, to close all of the pores of these accessible surfaces and to make the chemical nature of the substrate uniform. The encapsulation can thus be carried out directly on the stacks, the coating being able to penetrate into all of the available cavities.

(60) Advantageously, a layer of parylene is deposited as the pretreatment layer 50, such as a layer of parylene C, of parylene D, a layer of parylene N (CAS 1633-22-3) or a layer comprising a mixture of parylene C, D, and/or N on the object. Parylene (also called polyparaxylylene or poly(p-xylylene)) is a dielectric, transparent, semi-crystalline material that has high thermodynamic stability, excellent resistance to solvents and a very low permeability. Via its properties, namely its barrier properties with regard to water, the parylene contributes to the insulation of the object from its outside environment. This layer of parylene protects the sensitive elements of the battery from their environment. This protection is increased when this pretreatment layer is made from parylene N. Alternatively, a pretreatment layer containing polyimide is deposited. This layer of polyimide protects the sensitive elements of the battery from their environment.

(61) In an alternative and particularly advantageous manner, the pretreatment layer 50 consists of a first layer of polyimide 50a, preferably approximately 1 μm thick on which a second layer of parylene 50b is deposited, preferably approximately 2 μm thick (cf. FIG. 29b). This protection is increased when this second layer of parylene 50b, preferably approximately 2 μm thick is made from parylene N. The layer of polyimide 50a associated with the layer of parylene 50b improves the protection of the sensitive elements of the battery from their environment.

(62) However, the inventors have observed that this pretreatment layer 50, when it is made from parylene, does not have sufficient stability in the presence of oxygen. When this pretreatment layer is made from polyimide, it does not have sufficient impermeability, namely in the presence of water. For these reasons the first layer of the encapsulation system 31 is deposited on this pretreatment layer 50 in such a way that the first encapsulation layer 31 coats the pretreatment layer 50. The pretreatment layer 50 is disposed between the object 1000 and the first layer of the encapsulation system 31 according to the invention.

(63) Advantageously, the first encapsulation layer 31 composed of an electrically insulating material, preferably inorganic, is deposited by a technique of conformal deposition, such as atomic layer deposition (ALD) on the pretreatment layer. Thus conformal covering of all of the accessible surfaces of the stack previously covered with the pretreatment layer is obtained; the first layer is preferably an inorganic layer. The growth of the layer deposited by ALD is influenced by the nature of the substrate. A layer deposited by ALD on a substrate having various zones of different chemical natures will have a non-homogenous growth, which can engender a loss of integrity of this protective layer.

(64) The techniques of deposition by ALD are particularly well adapted to covering surfaces having a high roughness in a totally impermeable and conformal manner. They allow to make conformal layers, free of defects, such as holes (layers called “pinhole free”, free of holes) and represent very good barriers. Their WVTR coefficient is extremely low. The WVTR (water vapor transmission rate) coefficient allows to evaluate the permeance to water vapor of the encapsulation system. The lower the WVTR coefficient, the more impermeable the encapsulation system.

(65) The first layer 31 can be made of ceramic material, made of glass material or made of glass-ceramic material, for example in the form of oxide, of the type Al.sub.2O.sub.3, of nitride, of phosphates, of oxynitride, or of siloxane. This first encapsulation layer 31 has a thickness of less than 200 nm, preferably between 5 nm and 200 nm, more preferably between 10 nm and 100 nm and even more preferably approximately fifty nanometers. It is preferred to deposit it by a technique of conformal deposition, such as by atomic layer deposition (ALD).

(66) This first layer 31 deposited by ALD on the polymer pretreatment layer 50 allows on the one hand, to ensure the impermeability of the structure, i.e. to prevent the migration of the water inside the object and on the other hand to protect the pretreatment layer 50, preferably of parylene and/or of polyimide from the atmosphere, namely from air and from humidity, from heat exposures in order to avoid its degradation. This first layer 31 improves the service life of the encapsulated battery.

(67) However, the layers deposited by ALD are very mechanically fragile and require a rigid bearing surface in order to ensure their protective role. The deposition of a fragile layer on a flexible surface would lead to the formation of cracks, engendering a loss of integrity of this protective layer.

(68) Advantageously, a second encapsulation layer 32 is deposited on the first encapsulation layer 31 in order to increase the protection of the battery cells from their outside environment. Typically, this second layer 32 is made of polymer, for example made of silicone (deposited for example by impregnation or by plasma-assisted chemical vapor deposition using hexamethyldisiloxane (HMDSO)), or made of epoxy resin, or made of parylene, or made of polyimide, preferably made of parylene and/or made of polyimide as indicated above. According to the first alternative of the invention, the second encapsulation layer 32 is coated with a third layer 33, which protects it from the air and improves the service life of the object (in this case of the battery). Advantageously this third barrier layer 33 is also chosen in order to resist a high temperature, and has a mechanical strength sufficient to protect it during the later use of the object. Advantageously, the thickness of the third covering thin film is between 1 μm and 50 μm. Ideally, the thickness of the third covering thin film is approximately 10-15 μm, such a range of thickness allows to protect the battery against mechanical damage. The thickness of the third thin film 33 can be, preferably less than 10 μm, preferably less than 5 μm and even more preferably approximately 2 μm.

(69) This third layer 33 preferably contains epoxy resin, polyethylene naphthalate (PEN), polyimide, polyamide, polyurethane or silicone. Advantageously the materials used to make this third layer are chosen in order to facilitate the assembly of the electronic or electrochemical component. Advantageously, this third layer 33 is deposited via dipping.

(70) Second Alternative of the Invention

(71) This second advantageous alternative of the invention can be implemented indifferently with one or the other of the embodiments described below.

(72) According to a second alternative of the invention, the object can be encapsulated by an alternating succession of layers of parylene and/or of polyimide, having a thickness preferably between 2 μm and 10 μm, preferably between 2 μm and 5 μm and even more preferably approximately 3 μm, and of layers composed of an electrically insulating material having a thickness between 10 nm and 100 nm, preferably of approximately 50 nm, such as inorganic layers deposited conformally, preferably by ALD, as described above in order to create a multilayer encapsulation system.

(73) In order to improve the performance of the encapsulation, a pretreatment of the object can be carried out before its encapsulation by the encapsulation system according to the invention. This pretreatment of the object involves covering the object with a polymer layer (pretreatment layer 50), preferably containing polyimide and/or parylene, preferably parylene, namely parylene N in order to improve the protection of the object as indicated in the first alternative.

(74) Advantageously, a layer of parylene can be deposited as the pretreatment layer 50, such as a layer of parylene C, of parylene D, a layer of parylene N (CAS 1633-22-3) or a layer comprising a mixture of parylene C, D, and/or N on the object. Via its properties, namely its barrier properties with regard to water, the parylene contributes to the insulation of the object from its outside environment. This layer of parylene protects the sensitive elements of the battery from their environment. This protection is increased when this pretreatment layer 50 is made from parylene N.

(75) Alternatively, a pretreatment layer 50 containing polyimide can be deposited. This layer of polyimide protects the sensitive elements of the battery from their environment.

(76) In an alternative and particularly advantageous manner, the pretreatment layer 50 consists of a first layer of polyimide 50a, preferably approximately 1 μm thick on which a second layer of parylene 50b is deposited, preferably approximately 2 μm thick. This protection is increased when this second layer of parylene, preferably approximately 2 μm thick is made from parylene N. The layer of polyimide associated with the layer of parylene improves the protection of the sensitive elements of the battery from their environment.

(77) The object thus covered by this pretreatment layer 50 is then covered by an alternating succession of at least one first layer 31a composed of an electrically insulating material, preferably an inorganic layer, preferably having a thickness between 10 nm and 100 nm, preferably of approximately 50 nm, deposited conformally by ALD and of at least one second layer of the encapsulation system 32a according to the invention, preferably containing parylene and/or polyimide, preferably approximately 3 μm thick deposited on at least the first layer 31a.

(78) Advantageously, a third encapsulation layer 33 is deposited on this alternating succession of at least one first layer 31a, 31b, 31n and of at least one second layer 32a, 32b, 32n of the encapsulation system according to the invention, in such a way that the object is encapsulated in the encapsulation system 30 according to the invention comprising the three successive layers mentioned above (cf. FIGS. 30a and 30b). Advantageously, the third encapsulation layer 33 allows to increase the protection of the battery cells from their outside environment and to protect them against mechanical damage. This third and last encapsulation layer 33 has a thickness of approximately 10-15 μm. Typically, this third and last layer is made of polymer, for example made of silicone (deposited for example by dipping or by plasma-assisted chemical vapor deposition using hexamethyldisiloxane (HMDSO)), or made of epoxy resin, or made of parylene, or made of polyimide. For example, a layer of silicone (typical thickness approximately 15 μm) can be deposited by injection in order to protect the battery against mechanical damage. The choice of such a material comes from the fact that it resists high temperatures and the battery can thus be easily assembled by welding on electronic cards without the appearance of glass transitions.

(79) Third Alternative of the Invention

(80) This third advantageous alternative of the invention can be implemented indifferently with one or the other of the embodiments described below.

(81) Advantageously, the object is covered by a pretreatment layer 50 as indicated above, and is then covered by an alternating succession of a first layer 31a composed of an electrically insulating material, preferably an inorganic layer, preferably having a thickness between 10 nm and 100 nm, preferably of approximately 50 nm, deposited conformally by ALD, then of a second layer 32a, preferably containing parylene and/or polyimide as indicated above in the context of the previous alternatives, preferably approximately 3 μm thick deposited on at least the first layer, then of a new first layer 31b composed of an electrically insulating material, preferably an inorganic layer, preferably having a thickness between 10 nm and 100 nm, preferably of approximately 50 nm, deposited conformally by ALD on the second layer 32a, and then of a new second layer 32b, preferably containing parylene and/or polyimide, preferably approximately 3 μm thick deposited on at least the new first layer 31b. The object thus covered is then coated by a last layer corresponding to the third layer of the encapsulation system 33 according to the invention (cf. FIGS. 31a and 31b). Typically, this third and last layer is made of polymer, for example made of silicone (deposited for example by dipping or by plasma-assisted chemical vapor deposition using hexamethyldisiloxane (HMDSO)), or made of epoxy resin, or made of polyimide, or made of parylene. Advantageously, the thickness of the third layer of the encapsulation system 33 is between 1 μm and 50 μm. Ideally, the thickness of the third covering thin film 33 is approximately 10-15 μm, such a range of thickness allows to protect the battery against mechanical damage. The thickness of the third thin film 33 can be, preferably, less than 10 μm, preferably less than 5 μm and even more preferably approximately 2 μm especially when it is desired to minimize the size of the battery and to preserve good protection of the battery against mechanical damage. This succession of layers allows to notably increase the protection of the object while preserving a relatively small thickness.

(82) Primary Superposition of Sheets of Anode and of Sheets of Cathode/Stack of Anode and of Cathode

(83) Advantageously, the object protected by the encapsulation system according to the invention is a battery and preferably an all-solid or quasi-solid battery as indicated below.

(84) In the present description, “all-solid” battery means a battery comprising at least a cathode thin film, an anode thin film and a thin film of solid electrolyte, each of the thin films having a very small number of pores.

(85) In the present application, an elementary cell of a battery, preferably an all-solid battery comprises, in an alternating manner, an anode and a cathode, each optionally consisting of a stack of thin films. The anode comprises at least one thin film of an active anode material and optionally a thin film of an electrolyte material. The cathode comprises at least one thin film of an active cathode material and optionally a thin film of an electrolyte material so that the elementary cell of a battery, preferably an all-solid battery successively comprises at least one thin film of an active anode material, at least one thin film of an electrolyte material and at least one thin film of an active cathode material.

(86) When the battery is obtained from an alternating succession of at least one anode and of at least one cathode, the anode advantageously comprises, successively: optionally a thin film of an electrolyte material, a thin film of an active anode material, a metallic thin film, a thin film of an active anode material, and optionally, a thin film of an electrolyte material.

(87) In the present application, the term “sheet of anode” will be used to designate this layer succession usable in order to create a primary superposition from which at least one unit battery will be later obtained, preferably a plurality of unit batteries.

(88) Likewise, the cathode advantageously and successively comprises: optionally a thin film of an electrolyte material, a thin film of an active cathode material, a metallic thin film, a thin film of an active cathode material, and optionally, a thin film of an electrolyte material,

(89) so that a battery, preferably an all-solid battery successively comprises at least one thin film of an active anode material, at least one thin film of an electrolyte material and at least one thin film of an active cathode material.

(90) In the context of the present invention the thickness of each of the thin films present in the battery, is less than 10 μm and preferably less than 5 μm.

(91) In the present application, the term “sheet of cathode” will be used to designate this succession of layers usable in order to create a primary superposition. The primary superposition comprises an alternating succession of sheets of cathode and of sheets of anode, from which at least one unit battery comprising a stack of at least one anode and of at least one cathode will be later obtained, preferably a plurality of unit batteries. Two adjacent sheets of this primary superposition define at least one protruding region, intended to form an accessible connection zone, as well as at least one set-back region, intended to form a covering zone, i.e. a zone covered by the encapsulation system or by one of the three alternatives of the encapsulation system. These protruding and set-back regions will be explained in greater detail with regard to two embodiments, which do not limit the invention.

(92) The present invention relates in particular to the encapsulation of all-solid lithium-ion batteries. The present invention also relates to the encapsulation of the lithium-ion batteries using at least one porous electrode and/or at least one electrolyte comprising a porous inorganic layer, the electrode and the porous inorganic layer having an interconnected network of open pores in which the average diameter D50 of the pores is between 2 nm and 80 nm, preferably between 2 nm and 50 nm, preferably between 6 nm and 30 nm, and even more preferably between 8 nm and 20 nm and the pores of which, because of their size, are capable of absorbing a liquid phase by simple capillarity and are impregnated with a phase carrying lithium ions, i.e. by an electrolyte, such as a solution formed by a lithium salt dissolved in an organic solvent or a mixture of organic solvents, and/or comprising a polymer containing at least one lithium salt possibly dissolved in an organic solvent or a mixture of organic solvents, and/or comprising at least one ionic liquid containing at least one lithium salt possibly dissolved in an organic solvent or a mixture of organic solvents. The liquid phase “nanoconfined” or “nanotrapped” in the porosities, preferably in the mesoporosities, can no longer come out again. This battery comprising such a porous electrode and/or such an electrolyte is thus considered to be quasi-solid. According to the invention, the encapsulation system according to the invention cannot be used on lithium-ion batteries using separators since they are not sufficiently rigid to undergo treatments under vacuum without being degraded.

(93) The all-solid batteries 1 have a rigid one-piece structure on which an encapsulation system 30 can be deposited (cf. FIG. 1). FIG. 3, just like FIG. 2, is a perspective view with a cut of an all-solid battery 1. It reveals the inner structure of the central element comprising an assembly of elementary cells 2 covered by an encapsulation system 30 according to the invention and interconnections 40. FIG. 4 shows in greater detail an all-solid battery comprising an anode 10 and a cathode 20, each consisting of a stack of thin films. The anode successively comprises a thin film of an electrolyte material 13, a thin film of an active anode material 12 such as Li4Ti5O12, a metallic thin film 11 (for example made of stainless steel), a thin film of an active anode material such as Li4Ti5O12 12 and a thin film of an electrolyte material 13.

(94) The cathode 20 successively comprises a thin film of an electrolyte material 23, a thin film of an active cathode material 22 such as LiMn2O4, a metallic thin film 21 (for example made of stainless steel), a thin film of an active cathode material 22 such as LiMn2O4) and a thin film of an electrolyte material 23, with it being understood that the battery comprises an alternating succession of at least one anode 10 and of at least one cathode 20, two adjacent sheets of which define at least one protruding region, intended to form an accessible connection zone and at least one set-back region, intended to form a covering zone, i.e. zone covered by the encapsulation system.

(95) This battery consists of an assembly of a plurality of elementary cells connected in parallel, is formed from thin films of anode and of cathode made preferably from materials that are dimensionally stable during the steps of charge and discharge of the battery.

(96) The active anode materials that can be used to carry out such a function include insertion materials of the type Li4Ti5O12, certain of the nitrides of the type Li3-xMxN in a limited range of lithium insertion, as well as other anodes of the type LiySiTON or Sn3N4.

(97) The lithium-insertion materials used to make the cathodes are often much more dimensionally stable than the anode materials. The oxides with a spinel structure such as LiMn2O4, LiMn1.5Ni0.5O4, as well as the structures of the olivine type such as LiFePO4 are particularly dimensionally stable, and their use is preferred in the context of the present invention.

(98) Likewise, these active anode and cathode materials are assembled using solid electrolytes in order to ensure a rigid and stable surface for the encapsulation and avoid the risk of deterioration of the latter during the cycles of use of the battery. These solid electrolytes can be polymers, ceramics, glasses, glass-ceramics and/or hybrid materials composed both of an organic and inorganic portion.

(99) In order to ensure excellent protection against the gases of the atmosphere, it is necessary to have a protective film that has an extremely low WVTR. According to the prior art, the best protection is provided by metallic films, however the latter cannot cover the entirety of the battery without short-circuiting the electrodes.

(100) After the stacking step (cf. FIGS. 4, 7 and 15) and before the addition of the interconnections, the stack is encapsulated in an encapsulation system according to the invention allowing to ensure the protection of the battery from the atmosphere.

(101) Encapsulation System

(102) The quality of the encapsulation is of crucial importance for lithium-ion batteries. The encapsulation system 30 according to the invention is chemically stable, resists a high temperature, provides protection against humidity and is impermeable to the atmosphere in order to carry out its role of barrier layer. It consists of a plurality of layers successively deposited on the stack (cf. FIGS. 5, 8, 27a, 27b, 28a, 28b, 29a, 29b, 30a and 30b), as described above.

(103) To do this, the encapsulation system according to the invention consists of a plurality of layers successively deposited on the object, namely on the portions of the object needing to be protected.

(104) This encapsulation system allows electrical insulation and impermeability of the electronic components or batteries while ensuring the possibility of being able to later electrically connect them to each other and/or to external connection points. This encapsulation system can also be carried out according to the first, the second or the third alternative of the invention.

(105) Interconnections

(106) After the step of encapsulation of the electronic or electrochemical component such as a battery by the encapsulation system or any one of its alternatives, interconnections are added in order to establish the electric contacts necessary for the correct operation of said component.

(107) The interconnections described below can be made on electronic or electrochemical components such as a battery, obtained according to the first or the second embodiment, and coated by the encapsulation system according to the invention or any one of its alternatives, insofar as these combinations are possible for a person skilled in the art.

(108) In order to make these interconnections 40, the stack coated by the encapsulation system or any one of its alternatives is cut according to cutting planes allowing to obtain unit battery components, with the exposure on each of the cutting planes of the (+) and (−) connections of the battery, namely in the protruding regions, so that the encapsulation system coats four of the six faces of said battery, preferably continuously, in order for the system to be able to be assembled without welding, the two other faces of the battery being later coated by the interconnections. Advantageously, the battery comprises interconnections where the cathode, respectively anode, current collectors are visible. Preferably, the anode connections and the cathode connections are located on the opposite sides of the stack. On and around these connections an interconnection system is deposited (cf. FIG. 6). The connections can then be metallized using plasma deposition techniques known to a person skilled in the art, preferably by ALD (cf. FIG. 6 or FIG. 10, reference 41) and/or by immersion in a conductive epoxy resin (loaded with silver—(cf. FIG. 6 or FIG. 10, reference 42) and/or a bath of molten tin (cf. FIG. 6 or FIG. 10, reference 43) or by electrolytic deposition. Preferably, the interconnections consist of a stack of layers successively comprising a first metallic covering thin film deposited by ALD 41, a second layer made of epoxy resin loaded with silver 42 deposited on the first layer and a third layer containing tin 43 deposited on the second layer.

(109) The first conductive layer deposited by ALD 41 is used to protect the section of the battery against humidity. This first conductive layer deposited by ALD is optional. It allows to increase the calendar service life of the battery by reducing the WVTR at the interconnection. The second layer made of epoxy resin loaded with silver 42, allows to obtain “flexibility” for the connections without breaking the electric contact when the electric circuit is subjected to thermal and/or vibration stresses.

(110) The third metallization layer containing tin 43 is used to reduce the WVTR, which increases the service life of the battery.

(111) In another embodiment, this third layer can be composed of two layers of different materials. A first layer 43a in contact with the layer made of epoxy resin loaded with silver 42. This layer is made of nickel 43a and is created by electrolytic deposition. The layer made of nickel is used as a thermal barrier and protects the rest of the component from diffusion during the steps of assembly by reflow. The last layer 43b, deposited on the layer made of nickel 43a is also a metallization layer, preferably made of tin in order to make the interface compatible of the assemblies via reflow. This layer made of tin can be deposited either by dipping in a bath of molten tin or by electrodeposition; these techniques are known as such.

(112) For certain assemblies on tracks made of copper via microwiring, it can be necessary to have a last metallization layer 43b made of copper. Such a layer can be created by electrodeposition in place of the tin.

(113) In another embodiment, the interconnections can consist of a stack of layers successively comprising a layer of epoxy resin loaded with silver 42 and a second layer containing tin or nickel 43 deposited on the first layer.

(114) In another embodiment, the interconnections can consist of a stack of layers successively comprising a layer of conductive polymer such as a layer made of epoxy resin loaded with silver 42, a second layer containing nickel 43a deposited on the first layer and a third layer containing tin or copper 43b.

(115) In a preferred embodiment, the interconnections can consist of various layers that are respectively, in a non-limiting manner, a layer of conductive polymer such as an epoxy resin loaded with silver, a layer of nickel and a layer of tin.

(116) The interconnections allow to connect the alternatingly positive and negative electric connections on each of the ends of the battery. These interconnections allow to carry out the electric connections in parallel between the various battery elements. For this, only the (+) connections stick out on one end (protruding region), and the (−) are available on the other ends (other protruding regions).

(117) A first embodiment, which can be combined with the encapsulation system according to the invention or any one of its alternatives, will now be described.

(118) Description of the Method for Manufacturing a Battery, Preferably an all-Solid Battery According to a First Embodiment

(119) FIG. 7 shows according to a first embodiment, just like FIG. 4, an all-solid battery comprising anodes 10 and cathodes 20, each consisting of a stack of thin films; the anodes and the cathodes are offset laterally in such a way as to form protruding regions RS, intended to form an accessible connection zone and set-back regions RR, intended to form a covering zone, i.e. a zone covered by the encapsulation system.

(120) In this first embodiment and advantageously, the encapsulation of the battery is carried out on four of the six faces of the stack with it being understood that the cathode sections appearing on a first face and the anode sections appearing on a second face are not covered by this encapsulation system in such a way as to facilitate the collection of current on the lateral sides. The encapsulation layers surround the periphery of the stack, the rest of the atmosphere protection being ensured by the layers obtained by the interconnections.

(121) Preferably the cathode and anode connections are offset laterally, which allows the encapsulation layer to function as a dielectric in order to prevent the presence of a short circuit on these ends.

(122) Once the stack has been made, and after the encapsulation of the stack, interconnections (electric contacts, cf. FIG. 6, reference 40) are added where the cathode, respectively anode current collectors are visible (not coated with insulating electrolyte). These contact zones can be on the opposite sides of the stack in order to collect the current (lateral current collectors) or on adjacent sides (cf. FIG. 9 A and FIG. 9 B).

(123) Advantageously, the battery according to the invention obtained from a primary superposition, comprising an alternating succession of sheets of anode and of sheets of cathode as indicated above, is characterized in that said encapsulation system or any one of the alternatives 1 to 3 of said encapsulation system according to the invention totally coats four of the six faces of said battery and partly coats the two laterally opposite remaining faces, said two remaining faces being partly coated by at least said first covering layer 31,31′ and at least said second layer 32,32′ and said two remaining faces comprising an anode connection zone and a cathode connection zone. The third covering layer of said encapsulation system has difficulty penetrating the primary superposition. Consequently, this third layer has difficulty covering the two laterally opposite remaining faces.

(124) Method for Simultaneously Manufacturing a Plurality of Batteries

First Embodiment

(125) In order to increase the yield of production of the batteries, preferably of the all-solid batteries, the simultaneous manufacturing of a plurality of all-solid batteries can be carried out using a primary superposition of alternating sheets comprising between several tens of and several hundred anodes defined according to a cutting plane in the shape of a U and of sheets comprising between several tens of and several hundred cathodes defined according to a cutting plane in the shape of a U (cf. FIG. 11, first embodiment). All these sheets have perforations at their four ends in such a way that when these perforations are superimposed, all the cathodes and all the anodes of these sheets are superimposed and offset laterally (cf. FIGS. 12 and 13, first embodiment).

(126) The encapsulation is then carried out as described above according to the arrows (F) present in FIGS. 12 and 13. These arrows indicate the zones covered by the encapsulation system according to the invention (set-back regions). The encapsulation system according to the invention fills the space present in the cutouts in the shape of a U positioned top to tail and offset as presented in FIGS. 12 and 13.

(127) Advantageously, the primary superposition of sheets of anode and of sheets of cathode can be covered with the encapsulation system according to the first or the second or the third alternative as indicated above.

(128) The primary superposition of sheets of anode and of cathode thus coated is then cut by any appropriate means in such a way as to expose the anode and cathode current collectors and obtain unit batteries.

(129) Interconnections (electric contacts, cf. FIG. 15, reference 40, 41′, 42′ and 43′) are added where the cathode, respectively anode current collectors are visible (not coated with insulating electrolyte). These contact zones are, preferably, disposed on the opposite sides of the stack of the battery in order to collect the current (lateral current collectors) or on adjacent sides.

(130) A second embodiment, which can be combined with the encapsulation system according to the invention or any one of its alternatives, will now be described.

Second Embodiment

(131) In another embodiment, the simultaneous manufacturing of a plurality of batteries, preferably of a plurality of all-solid batteries can be carried out using an alternating primary superposition of sheets comprising between several tens of and several hundred anodes 10′ having notches 50, 50′ and of sheets comprising between several tens of and several hundred cathodes 20′ having notches 50″, 50′″. All these sheets have notches, preferably concentric orifices or holes in such a way that when these perforations are superimposed, all the cathodes and all the anodes of these sheets define at least one protruding region RS, intended to form an accessible connection zone, as well as at least one set-back region RR, intended to form a covering zone, i.e. a zone covered by the encapsulation system (cf. FIGS. 16, 17, 18 and 19). In FIG. 16, each anode sheet comprises an alternating succession of holes having diameters D1 and D2 where D2 is a diameter smaller than D1 and each cathode sheet comprises an alternating succession of holes having diameters D2 and D1 where D2 is a diameter smaller than D1, in such a way that the holes present on the sheets of anode having a diameter D1 (respectively D2) and of cathode having a diameter D2 (respectively D1) are concentric. FIG. 19 shows a perspective view analogous to FIG. 16 illustrating on a greater scale the primary superposition of sheets of anode and of sheets of cathode, and namely the superposition of the concentric holes having different diameters D1 and D2 present on these sheets highlighting the protruding regions and the set-back regions.

(132) The primary superposition of sheets of anode and of sheets of cathode 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 method, 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 cells of the batteries from their outside environment, a third layer 33 comparable to the third layer 33′ deposited on the second encapsulation layer (cf. FIGS. 22 and 23).

(133) Alternatively, the primary superposition of sheets of anode and of sheets of cathode can be covered with the encapsulation system according to the first or the second or the third alternative as indicated above.

(134) The primary superposition of sheets of anode and of cathode thus coated is then perforated at the concentric perforations by any appropriate means in such a way that the diameter of these new perforations is between D1 and D2 and thus reveals for each hole, either the anode connections or the cathode connections, i.e. the (+) and (−) connections of the battery (cf. FIGS. 21A and 21B) in order to facilitate the collection of current in the lateral concentric holes.

(135) After a cut called tertiary, in a median portion of said primary superposition, unit batteries are obtained (cf. FIG. 20) and interconnections (electric contacts, cf. FIG. 24, reference 40, FIG. 27 reference 41′, 42′ and 43′) are added where the cathode, respectively anode current collectors are visible (not coated with insulating electrolyte). These contact zones are, preferably, disposed on the opposite sides of the stack of the battery in order to collect the current (lateral current collectors) or on adjacent sides (cf. FIGS. 24, 25 to 27).

(136) The connections are metallized using plasma deposition techniques known to a person skilled in the art, preferably by ALD (cf. FIG. 27, reference 41′) and/or by immersion in a conductive epoxy resin loaded with silver—(cf. FIG. 27, reference 42′) and/or a bath of molten tin (cf. FIG. 27, reference 43′). Preferably, the interconnections consist of a stack of layers successively comprising a first metallic covering thin film deposited by ALD 41′, a second layer made of epoxy resin loaded with silver 42′ deposited on the first layer and a third layer containing tin 43′ deposited on the second layer. The interconnections allow to connect the alternatingly positive and negative electric connections on each of the concentric ends. These interconnections allow to carry out the electric connections in parallel between the various battery elements. For this, only the (+) connections stick out on one concentric end, and the (−) are available on another concentric end.

EXAMPLES

(137) The invention is illustrated below by examples which do not however limit the invention. These examples relate to the preparation of an all-solid battery and to the encapsulation of such a battery.

(138) 1. Preparation of a Lithium-Ion Battery

(139) A suspension of the anode material at 10 g/l was obtained by grinding followed by dispersion of Li4Ti5O12 in absolute ethanol with addition of several ppm of citric acid. A suspension of cathode material at 25 g/l was obtained by grinding followed by dispersion of LiMn2O4 in absolute ethanol. The cathode suspension was then diluted in acetone down to a concentration of 5 g/l. The suspension of electrolyte material at 5 g/l was obtained by grinding then dispersion of a powder of Li3Al0.4Sc1.6(PO4)3 in absolute ethanol.

(140) For all these suspensions, the grinding was carried out in such a way as to obtain stable suspensions with a particle size of less than 100 nm.

(141) The negative electrodes were prepared by electrophoretic deposition of the nanoparticles of Li4Ti5O12 contained in the suspension previously prepared. The thin film of Li4Ti5O12 (thickness approximately 1 μm) was deposited on the two faces of the substrate. These negative electrodes were then annealed at 600° C.

(142) The positive electrodes were prepared in the same manner, by electrophoretic deposition using the suspension of LiMn2O4. The thin film of LiMn2O4 (thickness approximately 1 μm) was deposited on the two faces of the substrate. These positive electrodes were then annealed at 600° C.

(143) After annealing the negative electrodes and the positive electrodes were covered with a layer of Li3Al0.4Sc1.6(PO4)3 electrolyte by EPD. The thickness of the Li3Al0.4Sc1.6(PO4)3 was approximately 500 nm on each electrode. These films of electrolyte were then dried.

(144) The stack of the Li3Al0.4Sc1.6(PO4)3-coated anodes and cathodes was then created in such a way as to obtain a laterally offset multilayer stack (cf. FIG. 7). The entirety was then maintained under pressure for 15 minutes at 600° C. in order to carry out the assembly.

(145) 2. Encapsulation of the Battery

(146) The encapsulation system was then deposited on the preceding multilayer stack. A layer of alumina Al.sub.2O.sub.3 representing the first layer of the encapsulation system was deposited by ALD). The multilayer stack of the coated anodes and cathodes was introduced into the chamber of a Picosun™ P300 ALD reactor. The chamber of the ALD reactor was previously placed under vacuum at 5 hPa and at 180° C. and previously subjected for 30 minutes to a flow of trimethylaluminum (hereinafter TMA)—(CAS: 75-24-1), a chemical precursor of alumina under nitrogen containing less than 3 ppm ultra-pure water of type 1 (σ≈0.05 μS/cm) as a carrier gas at a flow rate of 150 sccm (standard cm3/min), in order to stabilize the atmosphere of the chamber of the reactor before any deposition. After stabilization of the chamber, a layer of Al2O3 of 100 nm was deposited by ALD.

(147) A film of parylene N 12 μm+/−2 μm thick was then deposited by CVD on this first layer of alumina.

(148) A third encapsulation layer was then deposited on this second layer. Said layer can be made from epoxy resin, polyethylene naphthalate (PEN), silicone, polyimide, polyamide or polyurethane. Preferably, it is made from an epoxy resin. This third layer was then hardened under ultraviolet radiation (UV) in such a way as to reduce the speed of degradation of the battery by atmospheric elements.

(149) 3. Creation of the Interconnections of the Battery

(150) The stack thus encapsulated was then cut along cutting planes allowing to obtain a unit battery, with the exposure on each of the cutting planes of the cathode, respectively anode current collectors of the battery. The encapsulated stack was thus cut on two of the six faces of the stack in such a way as to reveal the cathode, respectively anode current collectors. Interconnections were then added where the cathode, respectively anode current collectors are visible (not coated with insulating electrolyte).

(151) The connections were then made electrically conductive, preferably metallized, by atomic layer deposition (ALD). This first interconnection thin film can namely be metallic or contain metallic nitride. This first interconnection layer was then immersed in a conductive epoxy resin (loaded with silver) then immersed in a bath of molten tin.

(152) The battery thus obtained was cycled between 2 and 2.7V.

LIST OF REFERENCE SYMBOLS

(153) 1 All-solid battery 2 Elementary cell 3 Stack of sheets of anodes and of cathode 10, 10′ Anode 11, 11′ Thin film of a conductive substrate (e.g., stainless steel) 12, 12′ Thin film of an active anode material 13, 13′ Thin film of an electrolyte material 20, 20′ Cathode 21, 21′ Thin film of a conductive substrate (e.g., stainless steel) 22, 22′ Thin film of an active cathode material 23, 23′ Thin film of an electrolyte material 30, 30′ Encapsulation system 31, 31′, 31a, 31b, 31n 1st covering thin film 32, 32′, 32a, 32b, 32n 2nd covering layer 32′″, 32″″ Layers capable of forming 2nd covering layer 33, 33′ 3rd covering layer 40, 40′ Interconnections 41, 41′ Metallic layer deposited by ALD 42, 42′ Layer made of epoxy resin loaded with Ag 43, 43′ Metallization layer (tin) 43a First metallization layer 43b Second metallization layer 50 Pretreatment layer 50a First pretreatment layer 50b Second pretreatment layer 1000 Object (e.g., electronic or electrochemical component) F Arrow indicating the zones covered by encapsulation system RS Protruding region RR Set-back region ZRT Covering zone ZC Connection zones III through XII Magnifications II-II, XII-XII, XIX-XIX Axes XIX′-XIX′, XXI-XXI Axes XXI′-XXI′, XXV-XXV Axes XXV′-XXV′ Axes