Storage device and manufacturing process

Abstract

Title: Storage Device and Manufacturing Method The invention relates to a method for manufacturing a solid-state battery electrode comprising at least the following steps: manufacturing an electrode (30) on a support, the electrode (30) having an upper face (31) opposite the support, the electrode (30) having at least one cavity (33) extending inward from its upper face (31), forming an ionically insulating layer, called a barrier layer (40), on the upper face (31) of the electrode (30) and in at least one cavity (33), then removing the barrier layer (40) so as to expose the upper face (31) of the electrode (30), while leaving in place the portion of the barrier layer (40) extending into at least one cavity (33). Figure for the abstract: Fig. 5C

Description

Title of the invention: Storage device and manufacturing method technical field

[0001] The present invention relates to microelectronic devices having electrodes, in the field of electrochemical energy storage, particularly in the form of microbatteries (thus creating an electrochemical microstorage component). The invention finds application in the manufacture of microelectronic devices offering such storage. A microelectronic device is understood to mean any type of device made using microelectronics. These devices include, in particular, in addition to purely electronic devices, micromechanical or electromechanical devices (MEMS, NEMS, etc.) as well as optical or optoelectronic devices (MOEMS, etc.). This includes applications such as electrochemical microstorage components (microbatteries, microsupercapacitors, solid ionic components of all types).

[0002] A specific interest of the invention is therefore the realization of electrochemical energy storage devices. This includes, in particular, battery-type devices, and especially those at the microelectronic scale, known as micro-batteries, accumulators, or capacitors using an electrolyte, preferably a solid one. PRIOR TECHNOLOGY

[0003] Electrochemical energy storage systems are generally implemented by successively depositing onto a substrate a first current collector, a first electrode, an electrolyte or ionic conductor, a second electrode, and a second current collector. Encapsulation, by means of depositing additional layers or by applying a protective cap, is often necessary to protect the system from chemical reactivity with oxygen and water vapor.

[0004] The miniaturization of devices implies the ability to produce small energy sources, particularly those a few square millimeters in size, capable of storing a sufficient amount of energy for the application. The capacity of a micro-battery is directly proportional to the volume of its two electrodes, and especially the positive electrode. The active surface area of ​​the latter is severely limited by the final size of the micro-battery so that it can be integrated into the final device without excessive bulk. Thus, one viable way to increase the capacity of a battery while minimizing its size is to increase the thickness of the electrode, and in particular the positive electrode. Typically, the goal is to exceed a thickness of 10 µm.

[0005] However, increasing this thickness leads to surface defects related to the deposition process, which can cause the energy storage device to short-circuit. In particular, electrode materials such as LiCoO2 are usually deposited by sputtering processes, which are constrained to thin layers, generally less than ten microns.

[0006] An attempt to solve the problem mentioned above is proposed in US publication 2021 / 0359339 A1, which suggests polishing the upper surface of the electrode. However, this solution is not satisfactory because when surface defects extend very deep into the electrode, the polishing must be effective to that same depth. This leads to a very significant reduction in the electrode thickness, which is counterproductive for the purpose of increasing battery capacity.

[0007] One object is therefore to propose a manufacturing process for electrodes which allows for large thicknesses without this being very detrimental, or even not detrimental, to the performance of the electrode, or even advantageous, especially from an electrical point of view.

[0008] Other objects, features and advantages will become apparent from an examination of the following description and accompanying drawings. SUMMARY

[0009] To achieve this objective, a first aspect of the invention relates to a method for manufacturing an electrode of a solid-state battery comprising at least the following steps: a. an embodiment of an electrode on a support, the electrode having an upper face opposite the support, the electrode having at least one cavity extending in a hollow from its upper face, b. the formation of an ionically insulating layer, called a barrier layer, on the upper surface of the electrode and in at least one cavity, c. a removal of the barrier layer so as to expose the upper face of the electrode, while leaving in place the portion of the barrier layer extending into at least one cavity.

[0010] The portion of the barrier layer left in place at the level of at least one cavity thus separates the electrode and the electrolyte at the level of that cavity. It therefore ensures local ionic isolation between these two layers. This makes it possible to limit or even prevent short circuits within a storage system comprising the electrode formed by the process described above. In particular, it is observed that this local ionic isolation makes it possible to avoid the appearance of areas of high electric field concentration during the operation of the storage system, areas which are very detrimental to system performance. The barrier layer also prevents the materials forming the electrolyte and the electrode from cracking under the effect of these high currents.

[0011] The local ionic isolation between the electrode and the electrolyte is only effective at the cavities, allowing the ionic current to flow between these two layers across the rest of the electrode's upper surface. It is thus estimated that the exchange surface area between the electrode and the electrolyte lost due to ionic isolation represents less than 5% of the total surface area. This proportion is quite acceptable, especially when considered in light of the advantages provided by the isolation.

[0012] Furthermore, the proposed solution does not require reducing the electrode thickness, as is the case in existing solutions (notably US 2021 / 0359339 Al). It is possible that a small portion of the electrode thickness may be removed during the partial removal of the barrier layer, but this portion is very small relative to the total electrode thickness. In particular, in the process according to the invention, it is not necessary to remove the electrode over the thickness encompassing the cavities. The electrode thickness is thus largely, if not entirely, preserved, which is beneficial to the storage system's capacity.

[0013] A second aspect of the invention relates to a method for manufacturing an energy storage device by electrochemical means, comprising the production of at least one electrode by implementing the method according to the first aspect of the invention.

[0014] A third aspect of the invention relates to an electrochemical energy storage device, comprising stacked on a support a collector, an electrode and an electrolyte, in which the electrode includes at least one cavity formed in a hollow from an upper face of the electrode and in that an ionically insulating layer, called a barrier layer, fills at least partially the at least one cavity, the barrier layer thus locally separating the electrode and the electrolyte.

[0015] The advantages and technical effects described with reference to the process according to the first aspect of the invention apply mutatis mutandis to the process and device according to the second and third aspects of the invention. BRIEF DESCRIPTION OF THE FIGURES

[0016] The aims, objects, features and advantages of the invention will become clearer from the detailed description of an embodiment thereof, which is illustrated by the following accompanying drawings in which:

[0017] [Fig.1A] Figures IA and IB represent the growth of a defect during the formation of an electrode.

[0018] [Fig.1B]

[0019] [Fig. IC] The [Fig. IC] is a scanning electron microscopy (SEM) image of defects typically appearing during electrode growth.

[0020] [Fig.2A] Fig.2A illustrates the formation of a cavity in an electrode following the release of a defect.

[0021] [Fig.2B] Fig.2B illustrates the concentration of the electric field at the cavity during the operation of an energy storage system including the electrode of Fig.2A.

[0022] [Fig.3A] Figures 3A to 3F illustrate the different steps of an example of a process according to the present invention.

[0023] [Fig.3B]

[0024] [Fig.3C]

[0025] [Fig.3D]

[0026] [Fig.3E]

[0027] [Fig.3F]

[0028] [Fig.4A] The [Fig.4A] is an enlargement of figures 3C and 3D on the upper face of the electrode.

[0029] [Fig.4B] The [Fig.4B] is an enlargement of the [Fig.3F] on the upper face of the electrode.

[0030] [Fig.5A] Figures 5A to 5C illustrate an alternative embodiment in which the particles present in the cavities on the surface of the electrode are removed.

[0031] [Fig.5B]

[0032] [Fig.5C]

[0033] The drawings are given by way of example and are not limiting of the invention. They constitute schematic representations of principle intended to facilitate understanding of the invention and are not necessarily to scale with practical applications. In particular, the dimensions are not representative of reality. DETAILED DESCRIPTION

[0034] Before proceeding to a detailed review of embodiments of the invention, optional features that may be used in combination or alternatively are listed below:

[0035] According to one embodiment, the electrode is produced by physical vapor phase deposition or by electrochemical deposition.

[0036] According to one example, LiCoO2 is used to make the electrode.

[0037] According to a preferred embodiment, the process further comprises, prior to the barrier layer formation step, an electrode annealing step. This annealing step removes at least some of the particles located in the cavities. Such annealing, in particular, allows for the efficient removal of particles exhibiting the largest dimensions, which are the most problematic. Advantageously, annealing is carried out at a temperature greater than or equal to 300°C, for example, at a temperature approximately equal to 400°C. Alternatively, or in combination with the annealing step, particle removal can be achieved using ultrasound and / or mechanical action. This mechanical action can, for example, be carried out by abrasion (or scrubbing) using jets or brushes.

[0038] According to a preferred embodiment, the process further comprises, prior to the barrier layer formation step, a polishing step of the electrode from its upper surface. Polishing allows the particles located in the cavities to detach.

[0039] According to one example, the polishing step is configured to thin the electrode to a thickness greater than or equal to 100 nm, preferably greater than or equal to 500 nm, and / or less than or equal to 2 pm. For example, to a thickness substantially equal to 1 pm.

[0040] According to a preferred embodiment, the barrier layer removal step includes at least one of a mechano-chemical polishing step and a grinding step.

[0041] According to a preferred embodiment, the barrier layer removal step comprises the following steps: a. a deposit of a resin layer on the barrier layer, the portions of the resin layer overlying at least one cavity having a thickness greater than that of the portions of the resin layer not overlying at least one cavity, b. an etching of the resin layer and the barrier layer so as to expose the upper face of the electrode, while leaving in place the portions of the barrier layer extending into at least one cavity.

[0042] According to one example, the resin layer deposition is configured so that it has a thickness less than or equal to 2 micrometers in its portions not overhanging at least one cavity.

[0043] According to one example, the barrier layer has a thickness greater than or equal to 10 nm, preferably greater than or equal to 30 nm.

[0044] According to an example of the process for manufacturing a chemical energy storage device according to the invention, the latter further comprises forming a collector on the support and then producing the electrode on the collector.

[0045] Certain parts of the device of the invention may have an electrical function. Some are used for ionic conduction properties, and the term electrode, collector, or equivalent means elements made of at least one material having sufficient ionic conductivity, in the application, to perform the function desired. Conversely, an ionic or dielectric insulator is understood to be a material which, in the application, provides an ionic insulation function.

[0046] An electrochemical energy storage device is defined as a device operating with an electrolyte layer, preferably in solid form, and enabling, in conjunction with a lower ionically conductive functional part and an upper ionically conductive functional part framing the electrolyte layer, the storage of energy in the form of an increase in potential difference or the release of energy in the form of a reduction in potential difference. In the field of microelectronics, this may refer to micro-batteries, which are understood to be such devices with dimensions on the microelectronic scale, in particular with an overall thickness of a few tens of microns, for example less than 100 microns.

[0047] Generally speaking, an electrochemical energy storage device comprises two electrodes separated by an electrolyte. During discharge, the anode (negative electrode) undergoes oxidation; ions pass through the electrolyte and travel to the cathode (positive electrode) to undergo reduction by intercalating into a specific material (host material); the electrons thus produced supply energy to the external circuit. During charging, the ions follow the reverse path, with electrons being supplied by the external circuit.

[0048] The term "selective etching with respect to" or "etching exhibiting selectivity with respect to" means an etching configured to remove a material A or a layer A with respect to a material B or a layer B, and having an etching speed of material A greater than the etching speed of material B. The selectivity is the ratio between the etching speed of material A and the etching speed of material B. The selectivity between A and B is denoted SA:B.

[0049] It is specified that, within the framework of the present invention, the terms "on", "overcomes", "covers", "underlying", "opposite" and their equivalents do not necessarily mean "in contact with". Thus, for example, the depositing, transferring, gluing, assembling or applying a first layer on a second layer does not necessarily mean that the two layers are directly in contact with each other, but means that the first layer at least partially covers the second layer by being either directly in contact with it or by being separated from it by at least one other layer or at least one other element.

[0050] A layer may also be composed of several sub-layers of the same material or of different materials.

[0051] A substrate, layer, or device "based" on a material M is understood to mean a substrate, layer, or device comprising only that material M or that material M and possibly other materials, for example alloying elements, impurities or dopant elements.

[0052] A coordinate system, preferably orthonormal, comprising the X, Y, Z axes is represented in [Fig.3A]. This coordinate system is applicable by extension to the other figures.

[0053] In this patent application, the terms thickness for a layer and height for a structure or device will be preferred. Height is measured perpendicular to the transverse plane XY. Thickness is measured in a direction normal to the principal plane of extension of the layer. Thus, a layer typically has a thickness along Z when it extends mainly along the transverse plane XY, and a projecting element, for example a trench, has a height along Z. The relative terms "on," "under," and "below" preferentially refer to positions measured along the Z direction.

[0054] The terms "approximately", "about", "in the order of" mean "to within 10%, preferably to within 5%".

[0055] Figures IA to 2B illustrate the drawbacks of the prior art. In particular, [Fig. 1A] shows the beginning of the formation of an electrode 30' on a stack consisting of a support 10' and a collector 20'. As illustrated, in a completely conventional manner, at least one defect 34' appears during the deposition of the electrode 30'. During the deposition of the electrode 30', this defect 34' grows and eventually extends to the upper face 31' of the electrode 30'. A SEM view of such a 34' defect is shown in [Fig.lC] extracted from the publication Influence of Growth Defects on the Corrosion Resistance of Sputter-Deposited TiAIN Hard Coatings, Panjan et al, Coatings 2019. As stated above, such a 34' defect can lead to the short-circuiting of the energy storage device.It is noted in particular that these defects can appear very early in the growth of the electrode and therefore extend over a very large part of the height of the electrode, which is very detrimental and promotes short circuits.

[0056] Furthermore, as illustrated in [Fig. 2A], the defects 34' can be removed by deliberate external intervention or detach spontaneously, for example, under the effect of one or more process steps. This creates a cavity 33' typically exhibiting a very high aspect ratio. After the formation of an electrolyte 50' and a second electrode 60' on the upper face of the electrode 30' and within the cavity 33', the electric field is found to be highly concentrated at the bottom of the cavity 33'. This is very detrimental to the operation of the storage system and can, in particular, induce short circuits. Specifically, this phenomenon can induce the formation of dendrites, for example of lithium, in the electrolyte, which leads to a short circuit.

[0057] It is these disadvantages that the present invention seeks to limit or even eliminate.

[0058] Different embodiments of the process according to the invention will now be described with reference to figures 3A to 5C.

[0059] A support 10 is first provided. This support 10 has an upper face 11 extending mainly in a plane parallel to a transverse plane XY. The transverse plane XY is defined by a first direction X and a second direction Y. The support 10 is, for example, formed from a plate of a semiconductor material such as silicon or any other organic or inorganic material, for example, glass. If the support 10 is electrically conductive, it may include at least one electrically insulating surface layer.

[0060] Conventionally, a collector 20 is then formed on the upper face 11 of the support 10. For the purposes of this application, the term collector means a part of the device whose function is to connect an electrode to an element external to the device, that is to say, located outside the stack of layers of the device, which are generally encapsulated. Metals with good electrical conductivity properties can be used for this part. This is the case with platinum; less expensive materials, such as titanium, are also possible.

[0061] An electrode 30 is formed on the upper face 21 of the collector, opposite the support 10 (see [Fig. 3A]). The electrode is, for example, made of LiCoO2 (lithium cobalt dioxide). The electrode 30 is typically formed by physical vapor deposition (PVD) or by electrochemical deposition (ECD). The transition from [Fig. 3A] to [Fig. 3B] illustrates the progressive formation of the electrode by one of these methods. The various possible deposition methods all result in significant surface roughness of the electrode 30.

[0062] The electrode 30 has an upper face 31 opposite the support 10 and the collector 20. This typically extends in a plane parallel to the transverse plane XY.

[0063] It is understood that [Fig.3B] in particular is a schematic representation, not showing in particular the defects present at the level of the upper face of the electrode 30.

[0064] The electrode 30 has a thickness e30 measured perpendicular to its upper face 31 and therefore typically along the Z direction. The thickness e30 of the electrode is typically greater than 10 pm, preferably greater than 20 pm. In particular, it may be between 20 and 200 pm.

[0065] As illustrated in [Fig. 3C], a layer based on an ionically insulating material is formed on the upper face 31 of the electrode 30. This layer can, in particular be designated barrier layer 40. It can for example be based on at least one of the following materials: A12O3, TiO2, TiN, Ti, Al, Pt, SiN, SiON, TaN, Ta.

[0066] Typically, the barrier layer 40 is deposited conformally on the stack. Thus, initially, the barrier layer 40 is typically deposited on the upper face 21 of the collector 20 and the upper face 11 of the support 10 due to the retraction of the electrode 30 relative to the collector 20 and of the collector 20 relative to the support 10. It is then possible, as illustrated in [Fig. 3D], to remove a portion of the barrier layer 40, for example, the portion extending against the upper face 11 of the support 10. Advantageously, this removal exposes at least a portion of the upper face 21 of the collector 20.

[0067] The barrier layer 40 has a thickness e40 measured perpendicular to the upper face 31 of the electrode 30 and therefore typically along the Z direction. The thickness e40 of the barrier layer 40 is typically greater than 10 nm, for example substantially equal to 50 nm.

[0068] Figure 4A is an enlargement of Figures 3C and 3D at the upper face 31 of the electrode 30. It illustrates the defects present on the surface of the electrode 30. As illustrated, cavities 33 extend from the upper face 31 of the electrode 30. These cavities 33 define pits in the electrode 30. In some cavities 33, additional defects in the form of particles 34 may be found.

[0069] As illustrated, the deposition of the barrier layer 40 is configured so that it extends into the cavities 33. The barrier layer 40 also covers the particles 34 when they are present in the cavities 33. A deposition of the barrier layer by atomic layer deposition (ALD) is preferred, which allows conformal deposition to the bottom of the cavities 33, even when these have a high height / width ratio.

[0070] The barrier layer 40 is then partially removed so as to partially, and preferably completely, expose the areas of the upper surface 31 of the electrode 30 that are free of cavities 33. During this removal, a portion of the barrier layer 40 extending into the cavity or cavities 33 is retained. Thus, the portion of the barrier layer 40 retained during this partial removal step, referred to as the remaining barrier portion 40*, can be continuous (in the case of a single cavity present on the surface of the electrode 30) or discontinuous (in the case of several cavities). In the latter case, the remaining barrier portion 40* is formed of a plurality of portions, each extending into a cavity 33. Advantageously, the remaining barrier portion 40* completely covers each cavity 33.

[0071] Partial removal of the barrier layer 40 can be achieved in different ways.

[0072] According to one example, this removal is carried out by polishing, for example by chemical-mechanical polishing (CMP) or by grinding. The polishing can be effective over a thickness greater than the thickness of the barrier layer 40 and continue into the electrode. The polishing can, for example, be carried out over a thickness of 100 nm. It should be noted, however, that it is sufficient for the polishing to expose the upper surface 31 of the electrode 30.

[0073] According to another example, the removal of the barrier layer 40 is carried out by non-conformally depositing a layer of resin onto the barrier layer 40 and then etching the barrier layer 40 through this resin layer. The resin layer is thus deposited so that it has a first thickness in its portions not overhanging cavities 33 and a second thickness distinct from the first thickness in its portions overhanging the cavities 33. The resin layer is deposited so that the second thickness is greater than the first thickness, for example, at least twice the first thickness. For example, the first thickness may be less than or equal to 2 µm and the second thickness greater than or equal to 4 µm.An etching step is then performed, configured to stop when the first layer is completely removed and the upper face 31 of the electrode 30 is exposed. Since the second layer is thicker than the first, the areas of the barrier layer 40 located within the cavities 33 are not affected by the etching. This etching can stop simply by timing, or it can be selective with respect to the electrode material.

[0074] It is possible to combine these different removal techniques.

[0075] This gives us the stacking illustrated in [Fig.3E].

[0076] As illustrated in [Fig. 3F], conventionally, an electrolyte 50 and a second electrode 60 are then formed above the electrode 30. The electrolyte 50 can, for example, be made of amorphous lithium nitride phosphate (LiPON). The second electrode 60 can, for example, be made of titanium. The second electrode 60 here forms the anode, the cathode being formed by the electrode 30.

[0077] The remaining barrier portion 40* thus separates the electrode 30 and the electrolyte 50 at each cavity 33. It therefore ensures local ionic isolation between these two layers. This makes it possible to limit or even prevent short circuits within the storage system.

[0078] Figures 5A to 5C illustrate an advantageous embodiment of the process according to the invention. In this example, the particles 34 located in the cavities 33 are removed before the barrier layer 40 is formed.

[0079] It has indeed been observed that, during the partial removal of the barrier layer 40, the particles 34 present in the cavities 33 sometimes detached. The barrier layer Since 40 has been deposited on these particles 34, the detachment of these particles causes a local absence of the barrier layer at the bottom of the cavities 33. Insulation is therefore no longer provided locally in the cavities 33 where a particle 34 was present and subsequently detached. To prevent this, it is advantageous to include, before the deposition step of the barrier layer 40, a step for removing at least some of the particles 34.

[0080] To achieve this, it is possible, for example, to anneal the electrode ([Fig. 5B]). This annealing generates stresses in the particles 34 and the electrode 30, eventually causing the particles 34 to detach. This method will work particularly well in the case of an electrode formed from a material with a high coefficient of thermal expansion, such as LiCoO2.

[0081] It is also possible to implement a polishing step, which also has the effect of removing the particles 34. This polishing can, for example, be carried out on a thickness less than or equal to 1 pm.

[0082] Annealing and polishing can of course be combined to detach as many particles 34 as possible.

[0083] It is noted that an annealing step may be sufficient to remove the particles 34 that are most problematic for the operation of the storage system, i.e., those with the largest dimensions. Generally, it is considered that a particle 34 with a height less than or equal to 50% of the height of the electrode 30 is not problematic.

[0084] Another object of the invention relates to an electrochemical energy storage device. This device is illustrated in [Fig. 3F]. It comprises, in a stacked configuration: the support 10, the collector 20, the electrode 30, and the electrolyte 50. As described previously, the electrode 30 has at least one cavity 33 extending from its upper face 31. Furthermore, the device according to the invention includes the remaining barrier portion of the barrier layer as described previously, which thus separates, at the cavities 33, the electrode 30 and the electrolyte 50. This storage device can be obtained by implementing any one of the embodiments of the process described previously. In particular, the particles 34 present at the cavities 33 may or may not have been removed during the manufacture of the device.The final device may therefore or may not contain residues of particles 34 or even whole particles within the cavities 33 (enlargements of figures 4B or 5C).

[0085] In view of the various embodiments described above, it appears that the present invention offers an effective solution for improving the performance of an electrode, particularly within an electrochemical energy storage device. In particular, the invention limits short-circuit problems and cracks in the electrolyte and in storage systems in general allow the electrode to have a significant thickness (several tens or even hundreds of micrometers). This results in an improved storage capacity of the system and therefore a more efficient system.

[0086] The invention is not limited to the embodiments previously described and extends to all embodiments covered by the invention.

Claims

Demands

1. A method for making an electrode of a solid battery comprising at least the following steps: • making an electrode (30) on a support (10), the electrode (30) having an upper face (31) opposite the support (10), the electrode (30) having at least one cavity (33) extending hollowly from its upper face (31), • forming an ionically insulating layer, called a barrier layer (40), on the upper face (31) of the electrode (30) and in at least one cavity (33), • removing the barrier layer (40) so as to expose the upper face (31) of the electrode (30), while leaving in place the portion of the barrier layer (40) extending into at least one cavity (33).

2. Method according to the preceding claim, wherein the electrode (30) is produced by physical vapor phase deposition or by electrochemical deposition.

3. A method according to any one of the preceding claims, wherein LiCoO2 is used to make the electrode (30).

4. A method according to any one of the preceding claims, further comprising, before the barrier layer formation step (40), an electrode annealing step (30).

5. A method according to any one of the preceding claims, further comprising, before the barrier layer formation step (40), a polishing step of the electrode (30) from its upper face (31).

6. A method according to the preceding claim, wherein the polishing step is configured to thin the electrode (30) to a thickness greater than or equal to 100 nm and / or less than or equal to 2 pm.

7. A method according to any one of the preceding claims, wherein the barrier layer removal step (40) comprises at least one of a chemical-mechanical polishing step and a grinding step.

8. A method according to any one of claims 1 to 6, wherein the step of removing the barrier layer (40) comprises the following steps: • a deposit of a resin layer on the barrier layer (40), the portions of the resin layer overlying at least one cavity (33) having a thickness greater than that of the portions of the resin layer not overlying at least one cavity (33), • an etching of the resin layer and the barrier layer (40) so as to expose the upper face (31) of the electrode (30), while leaving in place the portions of the barrier layer (40) extending into at least one cavity (33).

9. A method according to the preceding claim, wherein the resin layer deposition is configured so that it has a thickness less than or equal to 2 micrometers in its portions not overriding at least one cavity (33).

10. A method according to any one of the preceding claims, wherein the barrier layer (40) has a thickness greater than or equal to 10 nm, preferably greater than or equal to 30 nm.

11. A method for manufacturing an energy storage device by electrochemical means, comprising the production of at least one electrode (30) by implementing the method according to one of the preceding claims.

12. Method according to the preceding claim, comprising forming a collector (20) on the support (10) and then making the electrode (30) on the collector (20).

13. Electrochemical energy storage device, comprising stacked on a support (10) a collector (20), an electrode (30) and an electrolyte (50), characterized in that the electrode (30) comprises at least one cavity (33) formed in hollow from an upper face (31) of the electrode (30) and in that an ionically insulating layer, called a barrier layer (40), fills at least partially the at least one cavity (33), the barrier layer (40) thus locally separating the electrode (30) and the electrolyte (50).

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