• 专利附录
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    • 专利摘要:
    An electrochemical device (1), such as a microbattery or an electrochromic system, comprising a stack of thin solid layers formed on a substrate (2), said stack comprising successively: a first current collector covering a portion of the substrate (2), - a first electrode (4) defining a pattern having a lower face, an upper face and side walls, the lower face of the pattern covering at least a portion of the first current collector (3), - a layer of electrolyte (5) configured to cover at least the top face and at least a portion of the side walls of the pattern of the first electrode (4), - a second electrode (6) completely covering the electrolyte layer (5) the thickness of the electrolyte layer (5) disposed between the side walls of the pattern of the first electrode (4) and the second electrode (6) being substantially equal around said pattern to within 20%; current sensor (7) completely covering the second electrode (6), the second current collector (7) and the second electrode (6) being electrically isolated from the first current collector (3) and the first electrode (4). The device comprises first and second electrical connection means connected respectively to the first current collector (3) and to the second current collector (7) and isolated from each other.
    公开号:FR3027737A1
    申请号:FR1460154
    申请日:2014-10-22
    公开日:2016-04-29
    发明作者:Sami Oukassi；Steve Martin
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] Electrochemical device, such as a microbattery or an electrochromic system, and its method of production.
    [0002] TECHNICAL FIELD OF THE INVENTION The invention relates to an electrochemical device, such as a microbattery or an electrochromic system, and to its method of production. The state of the art Microbatteries are defined as electrochemical all-solid generators formed by an active stack of thin layers which constitute the electrodes (positive and negative) separated by an electrolyte. The positive electrode is formed of a material having good ionic conductivity, for example titanium oxysulfide (TiOS) or a lithiated metal oxide, such as Li0002, LiNiO2, LiMn204. The electrolyte is an electrical insulator with a high ionic conductivity such as lithium oxynitride and phosphorus (LiPON), LiSON, LiBON, Li2SO4, LiNb03 ... The negative electrode consists of lithium metal or a lithiated material. The microbatteries also comprise metal current collectors, for example platinum or tungsten. All layers of the microbattery are in the form of thin films obtained by PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition). The total thickness of the stack with the encapsulation layers is of the order of 15 μm. The operating principle is based on the insertion-deinsertion (or intercalation-deintercalation) of cations, generally Lit, in the host structure (intercalation material, or conversion material, alloy, etc.). The performance of the cycling stability of a microbattery requires an excellent reversibility of the X ionic insertion. These performances depend on several parameters: the selection of the host materials (nature of the positive and negative electrodes) and of the electrolyte, the electrochemical equilibrium (capacitances, dopings and thicknesses of the electrodes), the architecture of the microbattery (positioning and covering of the electrodes) and the ratio between the surface of the positive electrode and the surface of the negative electrode.
    [0003] Three main configurations of microbattery architecture are described in the prior art. In the first configuration, one of the surfaces (areas) of the electrodes is greater than the other.
    [0004] The article by Son et al. (Journal of Power Sources 243 (2013) 641-647) recommends using in a Li-ion battery, an anode having a surface greater than or equal to that of the cathode to increase the life of the battery. Such a configuration is also described in EP 2 192 638 or in US 6,818,356 which shows a substrate 44 successively covered by a cathode 50, an electrolyte layer 42 and an anode 52. The electrolyte layer 42 covers the side walls and the upper face of the cathode 50. The anode 52 is deposited above the electrolyte layer 42. The anode 52 partially covers the electrolyte layer 42. Each electrode 50, 52 is The anode is positioned above the architecture of the microbattery and has a larger surface area than the surface of the cathode. Figure 1 shows schematically such a configuration. US 2014/0106203 also discloses a lithium battery having such an architecture. To improve the performance of the battery, this document recommends, in addition, that the anode does not completely cover the cathode, this makes it possible to reduce or even eliminate the short circuits between the anode and the cathode, and to improve the charging capacity of the battery. The length of the non-overlap is at least 1 OpM. Such a configuration is simple to implement. In a second configuration, and as shown diagrammatically in FIG. 2, the surfaces of the electrodes 104, 106 are identical and the surfaces 15 face each other, arranged parallel to the substrate 102. Each electrode 104, 106 is connected to a current collector 110, 112. The flanks of the electrolyte layer 108 are not covered by the electrodes 104, 106. A portion of the current collector 112 of the electrode, disposed at the top of the stack, covers the flank electrolyte. US 2010/0330411 describes this architecture. However, such an architecture does not have a satisfactory life. In a third configuration, shown diagrammatically in FIG. 3, the stack deposited on the substrate 220 comprises two electrodes 226, 236 25 connected to current collectors 224, 230; the surface of the electrodes is identical and a dielectric material 242 is disposed at the sidewalls of the battery to isolate the electrolyte 238 from the current collector 230 of the electrode disposed above the electrolyte. U58420252 discloses a microbattery structure according to this configuration. However, such a configuration is more complex to implement and the life of these devices is not satisfactory either.
    [0005] This problem is also found in electrochromic systems. Electrochromic devices, or electrochromic devices are devices that are colored by the action of an electric field.
    [0006] The devices have an architecture similar to microbatteries: they comprise an active electrode and a counter-electrode separated by an electrolyte. The active electrode is conventionally composed of an electrochromic material able to insert, reversibly and simultaneously, ions and electrons.
    [0007] The insertion of the ions must be reversible in order to obtain devices having a good stability in cycling. OBJECT OF THE INVENTION The object of the invention is to overcome the drawbacks of the prior art and, in particular, to propose an electrochemical device having a good stability in cycling.
    [0008] This object is achieved by an electrochemical device, such as a microbattery or an electrochromic system, comprising a stack of thin solid layers formed on a substrate, said stack comprising successively: a first current collector covering a portion of the substrate; first electrode defining a pattern having a lower face, an upper face and side walls, the lower face of the pattern covering at least a portion of the first current collector, - an electrolyte layer configured to cover at least the upper face and the at least a part of the side walls of the pattern of the first electrode, - a second electrode completely covering the electrolyte layer, the thickness of the electrolyte layer disposed between the walls of the pattern of the first electrode and the second electrode being substantially equal to said pattern to within 20%, a second current collector the second electrode, the second current collector and the second electrode being electrically isolated from the first current collector and the first electrode, said device comprising first and second electrical connection means respectively connected to the first and second current collectors; and isolated between them.
    [0009] This object is also achieved by a method of producing an electrochemical device comprising the following successive steps: - providing a substrate covered by a first current collector, - forming a first electrode on the first current collector, the first electrode defining a pattern having a lower face, an upper face and side walls, the lower face of the pattern covering at least a portion of the first current collector, - forming an electrolyte layer on the first electrode, the electrolyte layer being configured to at least a portion of the sidewalls of the pattern of the first electrode are covered with at least a portion of the electrode, the thickness of the electrolyte layer disposed between the walls of the the first electrode and the second electrode being substantially equal around said pattern at 20% p to form a second current collector completely covering the second electrode, the second current collector and the second electrode being electrically isolated from the first current collector and the first electrode, forming first and second electrical connection means, connected respectively to the first and second current collectors and isolated from each other.
    [0010] BRIEF DESCRIPTION OF THE DRAWINGS Other advantages and features will emerge more clearly from the following description of particular embodiments of the invention given as nonlimiting examples, and represented in the accompanying drawings, in which: FIGS 1 to 3 schematically represent, in section, an electrochemical device according to the prior art; FIG. 4 and FIGS. 7 to 9 show, schematically and in section, an electrochemical device according to various embodiments of the invention; FIGS. 5 and 6 show schematically, in plan view, two electrodes and an electrolyte layer according to various embodiments of the invention.
    [0011] Description of a preferred embodiment of the invention As illustrated in FIG. 4, the electrochemical device 1, such as a microbattery or an electrochromic system, comprises a stack of thin solid layers formed on a substrate 2. Particularly advantageous embodiment, the substrate is electrically insulating or has on the surface an electrically insulating layer. The substrate 2 is provided with a first face and a second face.
    [0012] The stack is deposited on the first face of the substrate 2, that is to say on the electrically insulating layer. The stack comprises successively: a first current collector 3, covering a portion of the substrate 2, a first electrode 4 defining a pattern having a lower face, an upper face and side walls, the lower face of the pattern covering at least a part of the first current collector 3, an electrolyte layer 5 configured to cover at least the upper face and at least a part of the side walls of the pattern of the first electrode 4, a second electrode 6 completely covering the layer of electrolyte 5, - a second current collector 7 at least partially covering the second electrode 6.
    [0013] By at least a part, it is meant that the electrolyte layer covers at least a portion of each of the sidewalls of the pattern of the first electrode 4. In a particular embodiment, the electrolyte layer 5 completely covers the sidewalls. of the pattern of the first electrode 4. According to a particular embodiment, the thickness of the electrolyte layer 5 disposed between the side walls of the pattern of the first electrode 4 and the second electrode 6 is substantially equal around said pattern at 20. % near.
    [0014] The thickness of the electrolyte layer 5 does not vary by more than 20% all around the pattern. By all around the pattern is meant around the side walls of the pattern: the electrolyte layer does not vary by more than 20% between the side walls of the pattern of the first electrode and the second electrode 6.
    [0015] The thickness of the electrolyte layer 5 corresponds to the minimum distance between the first and second electrodes 4 and 6, or between the two opposite faces of the electrolyte. Advantageously, the thickness of the electrolyte layer 5 does not vary by more than 20% both between the side walls of the pattern of the first electrode and the second electrode 6, but also between the upper face of the pattern and the second electrode. 6. For example, the thickness of the electrolyte layer 5 at the sidewalls of the pattern of the first electrode does not vary by more than 20% with respect to the thickness of the electrolyte layer at the level of the upper face of said pattern.
    [0016] This substantially constant distance between the first electrode 4 and the second electrode 6 makes it possible to have a uniformity of electrochemical behavior: the thicknesses of the upper face and the lateral faces of the electrolyte layer 5 being substantially the same, the diffusion is done in a uniform way.
    [0017] Preferably, the thickness of the electrolyte layer 5 does not vary by more than 10%. The covering of the walls of the first pattern, by the electrolyte layer 5, is advantageously symmetrical all around the pattern. The electrochemical flows are advantageously distributed homogeneously all around the pattern. By symmetrical all around the pattern is meant that the thickness of the electrolyte layer 5, measured in a plane parallel to the first face of the substrate 2, is substantially equal at all points.
    [0018] Preferably, the electrolyte layer 5 and the first current collector 3 completely encapsulate the pattern of the first electrode 4: the upper face 4a and the lateral faces 4c of the first electrode 4 are completely covered by the electrolyte layer 5 and there is contact between the electrolyte layer 5 and the first electrode 4. By contact, it is meant that there is no intermediate layer between the electrolyte layer and the first electrode. Preferably, the contact is continuous between the layers. The electrolyte layer 5 covers not only the upper face 4a but also all the lateral faces 4c of the first electrode. If the pattern defined by the first electrode has four side faces, the four side faces are covered and in contact with the electrolyte layer 5.
    [0019] The lower face 4b of the first electrode is in contact with the first current collector 3. It is not in contact with the electrolyte layer 5. By lower or internal face is meant the face of the layer which is arranged down the stack, that is to say towards the substrate. The upper or outer face corresponds to the opposite face. This configuration is particularly advantageous because the entire external surface of the electrolyte layer 5 is in contact with the second electrode and the entire outer surface of the first electrode 4 is in contact with the electrolyte. Compared to previous configurations, all available surfaces participate in electrochemical exchanges. For example, in the configurations of the prior art where a non-overlap zone of the electrolyte exists, at this non-overlap zone, there is no ion circulation. The zone of non-overlap can be the place of irreversible insertions, in the case where the ions manage to be inserted close to the limit of the zone of recovery but continue to diffuse in the electrode, and move away from this zone to finally no longer be possible to de-insert. The electrochemical performances are then reduced. This absence of ion circulation can lead to non-uniform behavior and the formation of mechanical stresses between the covered areas and the uncovered areas of the cathode. The mechanical stresses created can induce a morphological degradation (loss of adhesion, electronic contact failure, or delamination of the complete stack) which can be converted into electrical degradation as cycling progresses. It has been found that in configurations where the second current collector is directly in contact with the electrolyte, an electrode / electrolyte / current collector (commonly called Li-free) battery is formed which disrupts the operation of the battery. main electrode / electrolyte / electrode during cycling. This parasitic operation is detrimental to the proper functioning of the battery.
    [0020] It has also been discovered that the deposition of a dielectric layer disposed in contact with the electrolyte and the current collector and between these two elements can degrade the interfaces between the various thin layers of the stack and the battery materials. In addition, the presence of a dielectric layer in this type of architecture cancels any ion exchange at the flanks of the structure, resulting in a loss of active surface of the battery. Deposition of the dielectric layer on the sidewall can degrade the interfaces / materials of the battery and shorten the life of the devices.
    [0021] On the other hand, in the embodiments illustrated in FIGS. 4, 7 and 8, since the entire external surface of the first electrode 4 is covered by the electrolyte, the ion flux and the potential are more homogeneous at every point on the surface of the electrode. the first electrode 4. The uniformity of the ion exchange makes it possible to limit the mechanical stresses and / or makes it possible to stress more uniformly the host structure of the first electrode 4 and the second electrode 6, which has the consequence of minimizing the localized variations of mechanical, chemical, and electrochemical properties (respectively, for example, delamination, irreversible superlithiation, overvoltage). The device has a good stability in cycling. It is observed that the life of such a device is increased. In addition, since the side walls or flanks of the first electrode 4 also participate in the electrochemical reactions, the capabilities of the device are improved. It is then possible to make a device more compact and more efficient.
    [0022] The electrolyte layer 5 is in contact with the first current collector 3 and is configured to electrically isolate said first current collector 3 from the second electrode 6.
    [0023] Advantageously, the electrolyte layer 5 completely covers the first electrode 4 and the first current collector 3 to come into contact with the substrate. The perimeter of the electrolyte layer 5 is in continuous contact with the substrate 2. By continuous contact, it is meant that the periphery of the electrolyte layer 5 is continuously in contact with the substrate 2: there is no element separating the substrate and the periphery of the electrolyte layer. The continuous connection of the electrolyte 5 with the substrate makes it possible to completely encapsulate the first current collector and the first electrode 4 between the substrate 2 and the electrolyte 5, and to isolate them from the external medium.
    [0024] A similar structure is present with the second electrode 6 which completely covers the external surface of the electrolyte 5, ie the side walls and the upper face of the electrolyte layer 5 and there is contact between the second electrode 6 and the electrolyte 5. The periphery of the second electrode 6 is in continuous contact with the substrate 2, encapsulating, insulating and protecting the electrolyte 5 and the first electrode 6 from the external medium. Advantageously, a covering of the second electrode 6 with more than 90% allows for better distribution and collection of electrical charges. Preferably, a complete cover (100%) of the second electrode 6 also makes it possible to protect it from the external environment. The second electrode 6 is electrically separated from the first electrode 4 by the electrolyte layer 5, which prevents short circuits. The first electrode 4 has a lower face which at least partially covers the first current collector 3 which allows different configurations to be realized. In an embodiment illustrated in FIG. 7, the first electrode 4 has a lower face which partially covers the first current collector 3. Advantageously, the pattern formed by the first electrode 4 defines a continuous peripheral guard ring all around the first electrode 4 on the upper face of the first current collector 3. In this embodiment, the electrolyte layer 5 completely covers the upper face of the first electrode 4, the lateral faces of the first electrode 4, the lateral faces of the first current collector 3 and the peripheral guard ring. The electrolyte layer 5 is in contact with the first electrode 4 and the first current collector 3. The electrolyte layer 5 completely encapsulates the first electrode 4 by resting on the first current collector 3. In this case of FIG. the first electrode 4 is not in contact with the substrate 2. Advantageously, the guard ring has a constant width materialized by a constant distance between the lateral face of the first electrode 4 and the lateral face of the first collector 3. Alternatively, the coverage of the upper face of the first current collector 3 by the first electrode may be partial but without definition of a continuous peripheral guard ring, that is to say that the first collector 3 has at least one lateral face in the extension of a lateral face of the first electrode 4 and / or that the first electrode 4 protrudes beyond the pattern formed by the first electrode In another embodiment as shown in FIG. 4, the coverage of the upper face of the first current collector 3 by the first electrode 4 is complete but without the first electrode 4 overflowing beyond the first electrode 4. current collector 3. In other words, the side walls of the first current collector 3 are each in the extension of the side walls of the first electrode 4. This configuration allows maximum use of the substrate surfaces.
    [0025] In this case, there is an interface between the electrolyte 5 and the first current collector 3 only on the lateral faces of the first current collector 3. In another variant embodiment, not shown, the cover of the upper face of the first current collector 3 by the first electrode 4 is complete and the first electrode 4 protrudes beyond the pattern formed by the first current collector 3 without forming a protection all around the first current collector 3. In this case of figure, there is an interface between the electrolyte 5 and the first current collector 3.
    [0026] In still another embodiment not shown, the cover of the upper face of the first current collector 3 by the first electrode 4 is complete and the first electrode 4 protrudes beyond the first current collector 3 so as to avoid any contact between the first current collector 3 and the electrolyte 5. The first current collector 3 is separated from the electrolyte 5 by the first electrode 4. In another variant embodiment illustrated in FIG. 8, the first current collector 3 is buried in the substrate and preferably in the electrically insulating layer so that at least a portion of the side faces of the first current collector 3 is covered by the electrically insulating layer. As in the previous embodiments, the electrolyte layer 5 is deposited so as to completely cover the first electrode 4 and what is left uncovered from the first current collector 3, for example the guard ring. Advantageously, the electrolyte layer 5 also overflows on the substrate to provide electrical insulation between the first and second electrodes. Advantageously, the contacts are buried in the substrate and protected during the steps of the production process. They are, for example, protected from possible oxidation during a heat or chemical treatment. The pattern defined by the first electrode 4 can be of any shape, for example a cylinder, a cube or a block. Advantageously, and as shown in FIGS. 5 and 6, the first electrode 4, the electrolyte layer 5 and the second electrode 6 have the same shape seen from above. The top view is obtained along the axis AA 'of FIG. 4. Advantageously, the initial shape of the first electrode 4 is retained during the deposition of the electrolyte layer 5 and preferably during the deposition of the second electrode. 6. This conservation of the initial shape makes it possible to limit the differences in thicknesses between the faces, which facilitates the conservation of flow of currents and / or homogeneous ionic fluxes. By means of a compliant deposit, the deposited thickness of the electrolyte layer is identical on the horizontal and vertical faces. The thickness deposited is therefore the same in every respect. By means of the conformal deposition of the electrolyte, the minimum distance separating the internal face of the second electrode 6 and the external face of the first electrode 4 is equal to a first distance, at any point on the external face of the first electrode. which facilitates obtaining a homogeneous ionic flux in the electrolyte. In a particularly advantageous embodiment, the electrolyte layer and / or the second electrode are deposited in a conformal manner so that the material thicknesses deposited on the upper face and on the lateral faces are equal (FIG. 7). By equal thicknesses it is meant that the differences in thickness are less than or equal to 5% of the total thickness deposited. A conformal deposition of the electrolyte layer allows a very good homogenization of the ionic fluxes. A compliant deposition of the second electrode makes it possible to facilitate a good distribution of potentials over the entire interface between the electrolyte layer and the second electrode. For example, if the first electrode 4 has a cobblestone pattern, the electrolyte layer 5 will also have a tile shape, the pad being provided with a non-through hole of the shape and size of the first electrode , so that the first electrode 4 is nested in the electrolyte layer 5. The outer surface of the first electrode 4 is in contact with the inner surface of the electrolyte layer 5.
    [0027] As a variant illustrated in FIG. 4, it may be advantageous to deposit the electrolyte layer 5 in a non-conforming manner and / or to structure the electrolyte layer 5 so as to erase the relief formed by the peripheral guard ring.
    [0028] The top views shown in Figures 5 and 6 may represent devices shown in Figures 4, 7 and 8 for cutting. In these cases, if the first electrode 4 is formed on the substrate in the form of a block, the electrolyte layer 5 is also formed so that the assembly formed by the first electrode and the layer of electrolyte 4 is always in the form of a pad and that the lateral faces of the first electrode 4 are parallel to the lateral faces facing the electrolyte layer 5. It is also advantageous for the deposit the second electrode 6 as well as the second current collector 7.
    [0029] The initial shape, here a block, can grow homothetically as and when the deposits made, for example the electrolyte layer 5, the second electrode 6 and the second current collector 7.
    [0030] The thicknesses of the electrolyte layer 5 and the second electrode 6 may be completely independent of one another. In an advantageous embodiment, the deposits of the electrolyte layer 5 and the second electrode 6 are made in a conformal manner, so as to have an identical thickness at all points of the electrolyte. The sidewalls of the first electrode 4c, the outer surface of the electrolyte layer 5 and the outer surface of the second electrode 6 are regularly spaced apart. This makes it possible to obtain a uniform ionic conductivity at the level of the electrolyte, as well as diffusion kinetics and a uniform insertion state at the level of the second electrode.
    [0031] Preferably, the second current collector 7 completely covers the second electrode 6. In the case of a current collector partially covering the second electrode, the uncovered portion may not participate in ion exchange, which may lead to failures. A total recovery of the second electrode by the current collector avoids these failures and increase the performance and / or the lifetime of the device. The second current collector 7 and the second electrode 6 are electrically isolated from the first current collector 3 and the first electrode 4.
    [0032] The device comprises first and second electrical connection means, also called electrically conductive connectors or electrical connection elements 9, respectively connected to the first current collector 3 and to the second current collector 7. The first and second electrical connection means are isolated between them. They form electrode contacts.
    [0033] The first current collector 3 being encapsulated by the electrolyte layer 5 and the second electrode 6, it is not possible to pass current as in conventional architectures.
    [0034] The first current collector 3 comprises electrical connection elements 9 electrically connect the first current collector 3 to a remote contact socket or a contact located on the second face of the substrate.
    [0035] According to a first embodiment, the first and / or second electrical connection means may comprise conductive vias traversing the substrate and respectively electrically connecting the first and the second current collectors at the second face of the substrate.
    [0036] For example, as shown in Figures 4 and 7, it is particularly advantageous to provide that the first current collector 3 comprises an electrically conductive connector 9 passing through the substrate to form an electrode contact.
    [0037] The electrically conductive connector 9 passes through the substrate so as to allow a contact on the face opposite to the face comprising the first and second electrodes and the electrolyte layer, i.e. from the first face to the second face. In this architecture, the electrode contact is deported, which makes it possible to keep a compact electrochemical device with good resistance to cycling. In this configuration, it is also advantageous to contact the second current collector 7 with another electrically conductive connector 9 which also passes through the substrate, i.e. from the first face to the second face. In this way, all the contacts are arranged on the same face of the substrate. Alternatively, the first current collector contact 3 is on one side of the substrate and the second current collector contact 7 is on the opposite face.
    [0038] Transverse means that the electrically conductive connectors 9 are from the first face of the substrate to the second face of the substrate. The second face may comprise any device adapted to collect the electrical charges. The electrically conductive connectors can be connected by vias. These are perpendicular connections to the first and second faces and passing through the substrate. In the case of a silicon substrate, it is advantageous to have an electrically insulating material between the connector 9 and the substrate 2 to avoid any short circuit.
    [0039] According to another embodiment, the first and / or the second electrical connection means may comprise at least one electrical connection buried in the substrate with a resumption of contact on the first face of the substrate, ie on the face of the substrate comprising the stack.
    [0040] For example, as illustrated in Figure 8, the electrically conductive connector 9 is formed by a conductive track which travels inside the substrate, preferably within the electrically insulating layer. The conductive track opens on the first face to form the first collector contact remotely. The electrical connector 9 travels inside the substrate to open on the same face, that is to say the face that includes the first and second electrodes. This configuration allows a better protection of the current collector during technological steps necessary for the formation of the stack, such as a chemical attack, for example. Deposition of the active layers on a substrate, which does not have a topography in the initial state, advantageously makes it possible to avoid gating at the level of the current collector. The first current collector 3 and the electrical connector 9 can form a single element in this configuration. According to another embodiment, the second electrical connection means comprise at least one electrical contact recovery of the second current collector disposed on the substrate, this contact recovery being formed by an end of the thin layer forming the collector. As shown in FIG. 9, a layer of dielectric material 8 can be arranged to separate the second electrode 6 and the second current collector 7 from the first current collector 3. Advantageously, the layer of dielectric material 8 also makes it possible to separate the electrolyte layer 5 of the first current collector 3. Those skilled in the art can combine different embodiments with each other.
    [0041] According to a preferred embodiment, the device 1 is a microbattery. The first electrode 4 corresponds to the negative electrode or the positive electrode of the battery. The second electrode 6 corresponds to the other electrode. Preferably, the first electrode 4 is the positive electrode, i.e. the cathode, and the second electrode is the negative electrode, i.e. the anode. Different microbattery structures can be produced: a so-called lithium metal microbattery; in this case the anode, corresponding to the second electrode 6, is made of lithium, - a microbattery of lithium ion type; in this case the anode is an insertion material, alloy or conversion of lithium, The realization of a lithium-free battery can also be considered. In this case, there is no anode. The second electrode is not deposited before the second current collector 7, which is then deposited directly on the electrolyte 5. The lithium electrodeposits directly to the surface of the second current collector 7 in charge mode to form the second electrode 6 and is dissolved in discharge mode. Preferably, the device is a lithium-ion microbattery and the second electrode 6 is an anode made of lithium lithium insertion or conversion material, or a lithium alloy. According to another preferred embodiment, the electrochemical device 1 is an electrochromic system. The "all solid" electrochromic system is in the form of a stack of thin solid layers on a substrate 2. In particular, the electrochromic device comprises, successively from the substrate 2, a counterelectrode 4, an ionic conductive electrolyte 5 , an electrochromic active electrode 6.
    [0042] The electrochromic active electrode is formed of an electrochromic material capable of reversibly and simultaneously inserting ions and electrons. Under the effect of a potential difference applied between the active electrode and the counter-electrode, the ions are inserted into the electrochromic material of the active electrode to give a persistent coloration of the corresponding oxidation state. By applying reverse bias, the ions disinhibit the active electrode which returns to its initial oxidation state, colored or transparent. The oxidation states of the electrochromic material therefore correspond to the inserted and uninserted states and are of a distinct color when subjected to an appropriate power supply.
    [0043] Before applying the potential difference, the color displayed is that of the substrate, obtained by transmittance through the stack. After applying a potential difference between the active electrode and the counter-electrode, a display of a different color corresponding to that of the electrochromic material of the active electrode is obtained. The second electrode 6 and / or the first electrode 4 is an electrode made of tungsten oxide, iridium oxide, vanadium oxide or molybdenum oxide.
    [0044] The second electrode 6 is preferably tungsten oxide or molybdenum oxide. The ionic conductive electrolyte solid layer is based on lithium, for example lithium nitride (Li3N), LiPON, LiSiPON, or LiBON, etc. The specific ion is, advantageously, Li lithium ion. The Li + ion has a higher mobility than other ions such as sodium or silver because of the small size of the lithium ion, decreasing the response time of the electrochromic system. The counter-electrode, for example the first electrode 4, is for example, in iridium oxide, vanadium oxide.
    [0045] The system may also include a protective coating based on acrylic resin or epoxy. Advantageously, since the electrochromic active electrode 6 completely covers the electrolyte layer 5, there is no need to deposit an insulating layer on the electrolyte layer 5 in order to protect it.
    [0046] An external supply circuit can counterbalance the charges and ensure the electroneutrality of the electrochromic display device. The device is adapted to be used for display of static information, for example, for applications in the field of advertising. The electrochromic system has a high mobility of Li ions, the system is reliable and efficient. The implementation of this electrochromic system is simple, industrializable and suitable for large-area display systems.
    [0047] The method for producing the electrochemical device 1 comprises the following successive steps: - providing a substrate 2 covered by a first current collector 3, - forming a first electrode 4 on the first current collector 3, the first electrode 4 defining a pattern having a lower face, an upper face and side walls, the lower face of the pattern covering at least a portion of the first current collector 3, - forming an electrolyte layer 5 on the first electrode 4, the electrolyte layer 5 being configured to cover at least the upper face and at least a portion of the side walls of the pattern of the first electrode 4, - to form a second electrode 6 completely covering the electrolyte layer 5, the thickness of the electrolyte layer 5 disposed between the side walls of the pattern of the first electrode 4 and the second electrode 6 being substantially equal around said 20% pattern close, - form a second current collector 7 completely covering the second electrode 6, the second current collector 7 and the second electrode 6 being electrically isolated from the first current collector 3 and the first electrode 4, - to form first and second second electrical connection means, respectively connected to the first current collector and the second current collector, and isolated from each other.
    [0048] More particularly, a microbattery 1 can be made with the method comprising the following successive steps: - providing a substrate 2, for example a silicon substrate - making the electrical connectors 9 (vias) in the substrate, by methods based on the production of an etching mask, the etching of the substrate through the etching mask, for example by deep reactive ion etching (or DRIE for "Deep Reactive Ion Etching"), and the deposition of an electrically insulating material then of an electrically conductive material for filling the etching hole - forming the first current collector 3: - depositing a Ti / Pt bilayer of 20 nm / 100 nm thickness, respectively - structuring the bilayer, by forming a mask etching, followed by wet etching, in two successive aqueous solutions "aqua reggia" (for Pt) and NH4OH / H2O2 / H2O (for Ti), - forming the first electrode 4: he Li0002 of 1 Op M thick, - structure said layer, by a step of forming an etching mask, followed by wet etching, in an aqueous solution containing sulfuric acid H2SO4, - form the electrolyte layer 5: - deposit a LiPON layer (for "lithium phosphorus oxynitride") 1.5 μm thick, - structure the LIPON layer by a step of forming an etching mask, followed by etching wet, in an aqueous solution containing hydrogen peroxide H 2 O 2, - forming the second electrode 6: - depositing a silicon layer of 100 nm thick, - structuring the silicon layer, by a step of forming a mask etching, followed by wet etching, in an aqueous solution containing KOH, forming the second current collector 7: depositing a Cu layer of lpm thick, - structuring said layer, by a step of forming an etching mask, followed by wet etching, in a solution aqueous solution containing NH4OH.
    [0049] The deposits of the first current collector 3, the first electrode 4, the electrolyte thin film 5, the second electrode 6 and the second current collector 7 are advantageously produced by physical vapor deposition (or PVD for physical vapor deposition "in English) and, more particularly, by sputtering.
    [0050] The first current collector 3, the first electrode 4, the electrolyte layer 5, the second electrode 6 and the second current collector 7 may also be structured by a photolithography step followed by at least one wet etching step: the The method is advantageously easily industrializable.
    [0051] The electrochemical device obtained has an ionic flux, between the first electrode and the second electrode, at any point of the first electrode. The active surface of the device is increased. The architecture of the electrochemical device allows a very uniform ion exchange at the two electrodes, which improves the electrochemical properties of the microbattery during cycling. In addition, the uniformity of flux makes it possible to considerably reduce, or even eliminate, the mechanical stresses at the level of the first electrode, compared to a conventional structure.
    [0052] The electrochemical device has no morphological degradation (loss of adhesion, electronic contact failure, or delamination of the complete stack). The electrochemical performances are not degraded as and when cycling.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. An electrochemical device (1), such as a microbattery or an electrochromic system, comprising a stack of thin solid layers formed on a substrate (2), said stack comprising successively: a first current collector covering a portion of the substrate (2), - a first electrode (4) defining a pattern having a lower face, an upper face and side walls, the lower face of the pattern covering at least a portion of the first current collector (3), - a layer of electrolyte (5) configured to cover at least the top face and at least a portion of the side walls of the pattern of the first electrode (4), - a second electrode (6) completely covering the electrolyte layer (5), thickness of the electrolyte layer (5) disposed between the side walls of the pattern of the first electrode (4) and the second electrode (6) being substantially equal around said pattern to within 20%, - a second neck current reader (7) completely covering the second electrode (6), the second current collector (7) and the second electrode (6) being electrically isolated from the first current collector (3) and the first electrode (4), said device having first and second electrical connection means respectively connected to the first current collector (3) and the second current collector (7), and insulated from each other.
    [0002]
    2. Device (1) according to claim 1, characterized in that the cover of the walls of the first pattern, by the electrolyte layer (5), is symmetrical all around the pattern.
    [0003]
    3. Device (1) according to one of claims 1 and 2, characterized in that the electrolyte layer (5) and the first current collector (3) encapsulatetotalement the pattern of the first electrode (4), the layer electrolyte (5) being in contact with the first current collector (3) and being configured to electrically isolate said first collector (3) from the second electrode (6).
    [0004]
    4. Device (1) according to any one of claims 1 to 3, characterized in that the first and / or second electrical connection means comprise conductive vias through the substrate (2).
    [0005]
    5. Device (1) according to any one of claims 1 to 3, characterized in that the first electrical connection means comprise at least one electrical connection buried in the substrate (2).
    [0006]
    6. Device (1) according to any one of claims 1 to 3, characterized in that the second electrical connection means 15 comprise at least one electrical contact recovery of the second current collector (7) disposed on the substrate ( 2), this contact recovery being formed by an end of the thin layer forming the collector.
    [0007]
    7. Device (1) according to any one of claims 1 to 6, characterized in that the electrode pattern is a cylinder, a cube or a block.
    [0008]
    8. Device (1) according to any one of claims 1 to 7, characterized in that the device (1) is a lithium-metal microbattery and in that the second electrode (6) is a lithium anode. 25
    [0009]
    9. Device (1) according to any one of claims 1 to 7, characterized in that the device (1) is a lithium-ion microbattery and in that the second electrode (6) is an anode made of plastic material. insertion or conversion of lithium, or a lithium alloy. 30
    [0010]
    10. Device (1) according to any one of claims 1 to 7, characterized in that the device (1) is an electrochromic system and in that the second electrode (6) and / or the first electrode (4) is an electrode made of tungsten oxide, iridium oxide, vanadium oxide or molybdenum oxide.
    [0011]
    11. A method of producing an electrochemical device (1) according to any one of claims 1 to 10, characterized in that the method comprises the following successive steps: - providing a substrate (2) covered by a first current collector (3), - forming a first electrode (4) on the first current collector (3), the first electrode (4) defining a pattern having a lower face, an upper face and side walls, the lower face of the covering pattern at least a part of the first current collector (3), - forming an electrolyte layer (5) on the first electrode (4), the electrolyte layer (5) being configured to cover at least the upper face and the least part of the side walls of the pattern of the first electrode (4), - forming a second electrode (6) completely covering the electrolyte layer (5), the thickness of the electrolyte layer (5) disposed between the side walls s of the pattern of the first electrode (4) and the second electrode (6) being substantially equal around said pattern to 20%, - forming a second current collector (7) completely covering the second electrode (6), the second collector current (7) and the second electrode (6) being electrically isolated from the first current collector (3) and the first electrode (4), forming first and second electrical connection means, respectively connected to the first collector current and the second current collector, and isolated from each other.30
    [0012]
    Method according to claim 11, characterized in that the first current collector (3), the first electrode (4), the electrolyte layer (5), the second electrode (6) and the second current collector ( 7) are deposited by physical vapor deposition.
    [0013]
    13. Method according to one of claims 11 and 12, characterized in that the first current collector (3), the first electrode (4), the electrolyte layer (5), the second electrode (6) and the second current collector (7) are structured by a step of forming an etching mask followed by at least one etching step.
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    法律状态:
    2015-11-02| PLFP| Fee payment|Year of fee payment: 2 |
    2016-04-29| PLSC| Search report ready|Effective date: 20160429 |
    2016-10-28| PLFP| Fee payment|Year of fee payment: 3 |
    2017-10-31| PLFP| Fee payment|Year of fee payment: 4 |
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    EP15191107.0A| EP3012886B1|2014-10-22|2015-10-22|Electrochemical device, such as a microbattery or an electrochromic system, and method for manufacturing same|
    US14/920,409| US9882201B2|2014-10-22|2015-10-22|Electrochemical device, such as a microbattery or an electrochromic system, and fabrication method thereof|
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