MESOPOROUS ELECTRODES FOR THIN-FILM ELECTROCHEMICAL DEVICES

专利摘要:
A method of manufacturing a porous electrode in a thin layer, said electrode comprising a layer deposited on a substrate, said layer being binder-free and having a porosity of greater than 30% by volume, and preferably less than 50% by volume, and pore diameter of less than 50 nm, said method being characterized in that: (a) supplying a colloidal suspension comprising nanoparticle aggregates of at least one material P of average primary diameter D50 of less than or equal to 80 nm, and preferably less than or equal to 50 nm, said aggregates having a mean diameter of between 80 nm and 300 nm (preferably between 100 nm and 200 nm), (b) supplying a substrate, (c) depositing on said substrate a porous electrode layer, preferably mesoporous, by electrophoresis or dip-coating, from said colloidal suspension supplied in step (a), (d) drying said layer obtained in step (c), preferably under a stream of air, (e) optionally, consolidation of the porous electrode layer, preferably mesoporous obtained in step (d) by pressing and / or heating .
公开号:FR3080957A1
申请号:FR1853920
申请日:2018-05-07
公开日:2019-11-08
发明作者:Fabien Gaben
申请人:I TEN；
IPC主号:

专利说明:

POROUS ELECTRODES FOR THIN FILM ELECTROCHEMICAL DEVICES
Technical field of the invention
The invention relates to the field of electrochemistry, and more particularly to thin film electrochemical systems. It relates more precisely to thin film electrodes usable in electrochemical systems such as high power batteries (in particular lithium ion batteries), supercapacitors, fuel cells, and photovoltaic cells. It applies to anodes and cathodes. The invention relates to porous electrodes; they can be impregnated with a liquid electrolyte.
The invention also relates to a process for the preparation of such a porous thin film electrode, which uses nanoparticles of an electrode material, and the electrodes thus obtained. The invention also relates to a method of manufacturing an electrochemical device comprising at least one of these electrodes, and the devices thus obtained.
State of the art
There are many technologies for storing electrical energy; for a given application the choice depends mainly on the power requirement (expressed in W) and the energy requirement (expressed in Wh). For example, if you are looking for high power over a relatively short time, capacitors or supercapacitors can be a good solution. They consist of two porous electrodes (most often made of activated carbon to ensure good electronic conductivity) separated by an insulating membrane; the electrodes are immersed in an electrolyte which will form an electrical double layer on the surface of the electrodes capable of storing electrical energy. These devices are characterized by a very fast charging and discharging time.
The storage of electrical energy used in electric vehicles, mobile phones or computers must meet different needs, namely high power supplied over a fairly long time. Lithium ion batteries are often used. They consist of a positive electrode, an electrolyte and a negative electrode. During their operation, lithium ions are transported from one of the electrodes to the other through the electrolyte. During the discharge of the battery, an amount of lithium reacts with the active material of positive electrode from the electrolyte, and an equivalent amount of lithium ions is introduced into the electrolyte from the active material of the negative electrode, the concentration of lithium ions thus remaining constant in the electrolyte. The insertion of lithium into the material forming the positive electrode is compensated by the supply of electrons from the negative electrode via an external circuit; thus the battery can supply an electric current. During charging, the reverse phenomena take place.
The power density of lithium ion batteries is generally lower than that of supercapacitors because of the fairly slow diffusion of lithium ions in the thickness of the active materials (electrodes, electrolyte) and the transport time of lithium ions in the electrolyte. The storage capacity of a lithium ion battery depends among other things on its electrodes, in particular on the quantity of active material present within the electrodes and to a lesser extent on their thickness: at equal density and surface, the more the electrodes are thicker the greater the energy storage capacity of the battery. However, the internal resistance (series resistance) of the battery increases with the thickness of the layers.
To exceed the performance of conventional lithium ion batteries, materials with a high storage capacity and a high charge-discharge power are sought. More specifically, it is desired to have batteries with a high energy density, a high power density, and a long service life (expressed in calendar life and in number of discharge and charge cycles); for certain uses, batteries are sought which function well at very low temperatures (knowing that the series resistance internal to the battery increases when the temperature drops). In addition, the battery, given the large energy it is likely to store, must not present a safety risk in the event of a malfunction; for example, it should not ignite. And finally, the various constituents of a lithium battery must be chosen so as to be able to produce, with robust and inexpensive methods, batteries at low cost price.
Electrochemical cells are known, such as lithium ion batteries using particles of electrode active materials of micrometric size linked by an organic binder. WO 02/075 826 discloses electrodes for electrochemical cells made of a mesostructured electrode material and an organic binder. The organic binder being an electronic insulator, it is charged with carbon particles, an electronic conductor. These electrodes comprise a three-dimensional mesoporous structure which can be impregnated with an electrolyte so as to form a junction with a large specific surface. The three-dimensional structure of the electrode makes it possible to overcome the problem of ionic diffusion in the electrolyte, inherent in conventional electrodes with large active surface, and to ensure the interconnectivity as well as the access of the liquid organic electrolyte to the whole porous space. The mechanical stability of the structure is essentially ensured by the organic binder within the mesoporous electrode.
The presence of organic binder is an essential characteristic of the electrodes described in WO 02/075 826, but it has several drawbacks. The organic binder charged with electrically conductive particles can give rise to failures during thermal cycling: the particles of electrode material linked together by the organic binder can locally lose electrical contact, which leads to a gradual increase in resistance. battery series. The presence of an organic binder also limits the working temperature of the battery, and always poses a fire risk.
And finally, the presence of an organic binder may be incompatible with certain manufacturing processes, and in particular with those which involve vacuum deposition and / or deposition at high temperature. In particular, the presence of an organic binder does not allow subsequent deposition of a dielectric layer by the atomic layer deposition technique ("Atomic Layer Deposition" in English, hereinafter ALD) since the binder risks decompose and pollute the ALD reactor during deposition. Furthermore, the presence of a binder can prevent the coating produced by ALD from conforming and playing its role, i.e. blocking parasitic reactions that may occur between the electrodes and the electrolyte. However, the production of these deposits by ALD promotes the longevity of these electrodes, and a fortiori the durability over time of the batteries containing them. The presence of organic binder in a battery prevents its optimal encapsulation.
The present invention seeks to remedy at least in part the drawbacks of the prior art mentioned above.
More specifically, the problem that the present invention seeks to solve is to provide a method of manufacturing porous electrodes having a controlled pore density which is simple, safe, rapid, easy to implement, inexpensive and capable of being free from the use of organic binders and / or electronic conductive materials such as graphite.
The present invention also aims to provide safe porous electrodes having a high ionic conductivity, a stable mechanical structure, good thermal stability and a long service life.
Another object of the invention is to provide electrodes for batteries capable of operating at high temperature without problem of reliability and without risk of fire.
Another object of the invention is to provide porous electrodes which have, in addition to the above characteristics, a low interfacial resistance.
Another object of the invention is to provide porous electrodes impregnated with an electrolyte whose parasitic reactions are minimized.
Another object of the invention is to provide a method of manufacturing an electronic, electrical or electrotechnical device such as a battery, a capacitor, a supercapacitor, a photovoltaic cell comprising a porous electrode according to the invention.
Yet another object of the invention is to provide devices such as batteries, lithium ion battery cells, capacitors, supercapacitors, photovoltaic cells capable of storing high energy densities, of restoring this energy with very high power densities (especially in capacitors or supercapacitors), to withstand high temperatures, to have a long service life and which can be encapsulated by coatings deposited by ALD under high temperature.
Objects of the invention
According to the invention, the problem is solved by the use of at least one electrode which has a porous structure having a porosity greater than 30% by volume. Very preferably, this porosity is a mesoporosity. This electrode is deposited by electrophoresis from a colloidal suspension of nanoparticles of electrode material. Preferably it does not contain a binder. According to an essential characteristic of the invention, this suspension comprises aggregates of nanoparticles.
A first object of the invention is a method of manufacturing a porous electrode in a thin layer, said electrode comprising a layer deposited on a substrate, said layer being free of binder and having a porosity greater than 30% by volume, and pores with an average diameter of less than 50 nm, said method being characterized in that:
(A) a colloidal suspension is supplied comprising aggregates of nanoparticles of at least one material P with an average primary diameter D ₅₀ less than or equal to 80 nm, and preferably less than or equal to 50 nm, said aggregates having an average diameter included between 80 nm and 300 nm (preferably between 100 nm and 200 nm), (b) a substrate is supplied, (c) a layer of porous electrode, preferably mesoporous, is deposited on said substrate by electrophoresis or by the method coating by soaking (called "dip-coating" in English), from said colloidal suspension supplied in step (a), (d) drying said layer obtained in step c), preferably under a air flow.
A heat treatment step, possibly preceded by a pressure step, can be added after step (d), in order to improve the performance of the electrodes obtained. Depending on the materials used, this heat treatment (i.e. heating) can improve the texturing of the layer, improve the crystalline state of the layer, improve the sintering of nanoparticles, or even improve the adhesion of the layer to the substrate. The heat treatment can also be carried out at the same time as the pressure is applied.
Advantageously, the electrophoretic deposition is carried out in step c) by stationary galvanostatic electrodeposition or by galvanostatic electrodeposition in pulsed mode.
Advantageously, the total porosity of the porous electrodes does not exceed 50% by volume.
In one embodiment of this method:
(a1) a colloidal suspension comprising monodisperse nanoparticles of at least one material P with an average primary diameter D _{50 of} less than or equal to 80 nm, and preferably less than or equal to 50 nm, is supplied;
(a2) the monodisperse nanoparticles present in said colloidal suspension are destabilized so as to form aggregates of particles with an average diameter between 80 nm and 300 nm, preferably between 100 nm and 200 nm, said destabilization preferably taking place by addition a destabilizing agent such as a salt, preferably LiOH;
(b) supplying a substrate;
(c) a porous electrode layer is deposited on said substrate by electrophoresis or by dip-coating, from said colloidal suspension comprising the aggregates of nanoparticles obtained in step (a2);
(d) said layer is dried, preferably under an air flow, and a step (e) can be added after step (d) of consolidation of the porous electrode layer obtained in step (d) such as a pressing or heat treatment step (ie heating), possibly preceded by a pressure step, in order to improve the performance of the electrodes obtained. The heat treatment can also be carried out at the same time as the pressure is applied.
Said primary nanoparticles forming the aggregates are preferably monodisperse, that is to say their primary diameter has a narrow distribution. This allows better control of the porosity.
The heat treatment leads to the partial coalescence of the nanoparticles of material P (phenomenon called in English "necking") favoring the conduction of electrons between the nanoparticles, knowing that the nanoparticles have a high surface energy which is the driving force for this structural modification ; the latter occurs at a temperature much lower than the melting point of the material, and after a fairly short treatment time. Thus a three-dimensional porous structure is created within which the lithium ions exhibit mobility which is not slowed down by grain boundaries or layers of binder. Furthermore, the ionic conduction can also be ensured by the electrolyte impregnated in the electrode according to the invention. This structure also has good mechanical strength of the layer.
Aggregates can also be obtained directly after hydrothermal synthesis if the suspension is not sufficiently purified: the ionic strength of the suspension then leads to the aggregation of primary nanoparticles to form larger aggregated particles.
In a particular embodiment, a layer of a material is deposited after step (d) or after step (e), preferably by the technique of depositing ALD atomic layers. electrically insulating on and inside the pores of the porous layer, preferably mesoporous. This electrically insulating material can be chosen from AI ₂ O ₃ , SiO ₂ , ZrO ₂ . This coating coating typically has a thickness of between 1 nm and 5 nm. It makes it possible to reduce the interfacial faradaic reactions existing between the porous electrode layer and the electrolyte.
Alternatively, a layer of an ionic conductive material chosen from Li ₃ PO ₄ , Li, is deposited after step (d) or after step (e), preferably by ALD, during step (f). ₃ BO ₃ , lithium lanthanum zirconium oxide, preferably Li ₇ La ₃ Zr ₂ 0i ₂ , on and inside the pores of the porous layer, preferably mesoporous. This coating coating typically has a thickness of between 1 nm and 5 nm.
Another object of the invention relates to a porous, preferably mesoporous electrode usable in a lithium ion battery. Another subject of the invention relates to a porous, preferably mesoporous, electrode of porosity greater than 30% by volume comprising pores of average diameter less than 80 nm, preferably less than 50 nm, a primary diameter of particles less than 30 nm, preferably comprising a thickness of less than 10 μm, characterized in that it is free of binder.
Advantageously, said pores of the porous electrode, preferably mesoporous, are impregnated with an electrolyte, preferably a phase carrying lithium ions such as an ionic liquid containing lithium salts, possibly diluted in an organic solvent or a mixture of organic solvents containing a lithium salt which may be different from that dissolved in the ionic liquid.
Another object of the invention relates to a battery comprising at least one porous electrode capable of being obtained by the method according to the invention. Another object of the invention relates to a battery, all of the electrodes of which are porous electrodes capable of being obtained by the process according to the invention.
Brief description of the figures
Figures 1 and 2 illustrate different aspects of embodiments of the invention, without limiting its scope.
Figure 1 (a) shows a diffractogram, Figure 1 (b) a photograph obtained by transmission electron microscopy of primary nanoparticles used for depositing the electrodes according to the invention by electrophoresis.
Figure 2 illustrates nanoparticles before (Figure 2 (a)) and after heat treatment (Figure 2 (b)), illustrating the phenomenon of "necking".
detailed description
1. Definitions
For the purpose of this document, the size of a particle is defined by its largest dimension. By “nanoparticle” is meant any particle or object of nanometric size having at least one of its dimensions less than or equal to 100 nm.
By “mesoporous” materials is meant any solid which has within its structure pores called “mesopores” having a size intermediate between that of the micropores (width less than 2 nm) and that of the macropores (width greater than 50 nm), namely a size between 2 nm and 50 nm. This terminology corresponds to that adopted by IUPAC (International Union for Pure and Applied Chemistry), which is used by those skilled in the art. The term “nanopore” is therefore not used here, even if the mesopores as defined above have nanometric dimensions within the meaning of the definition of nanoparticles, knowing that the pores of size smaller than that of the mesopores are called by the skilled in the art of "micropores".
A presentation of the concepts of porosity (and of the terminology which has just been exposed above) is given in the article "Texture of pulverulent or porous materials" by F. Rouquerol et al. published in the "Engineering techniques" collection, Treatise on Analysis and Characterization, booklet P 1050; this article also describes the porosity characterization techniques, in particular the BET method.
For the purposes of the present invention, the term “mesoporous electrode” or “mesoporous layer” means an electrode, respectively a layer which has mesopores. As will be explained below, in these electrodes or layers the mesopores contribute significantly to the total pore volume; this state of affairs is translated by the expression “electrode or mesoporous layer of mesoporous porosity greater than X% by volume” used in the description below.
The term "aggregate" means, according to IUPAC definitions, a weakly bound assembly of primary particles. In this case, these primary particles are nanoparticles having a diameter which can be determined by transmission electron microscopy. An aggregate of aggregated primary nanoparticles can normally be destroyed (i.e. reduced to primary nanoparticles) suspended in a liquid phase under the effect of ultrasound, according to a technique known to those skilled in the art.
According to the invention, the porous, preferably mesoporous, electrode layer can be deposited electrophoretically or by dip-coating from a suspension of nanoparticle aggregates.
2. Preparation of nanoparticle suspensions
In the context of the present invention, it is preferable not to prepare these nanoparticle suspensions from dry nanopowders. They can be prepared by grinding powders or nanopowders in the liquid phase. In another embodiment of the invention, the nanoparticles are prepared in suspension directly by precipitation. The synthesis of nanoparticles by precipitation makes it possible to obtain primary nanoparticles of very homogeneous size with a unimodal size distribution, of good crystallinity and purity. In an even more preferred embodiment of the invention, the nanoparticles are prepared directly at their primary size by hydrothermal or solvothermal synthesis; this technique makes it possible to obtain nanoparticles with a very narrow size distribution, called "monodisperse nanoparticles". The size of these non-aggregated nanopowders / nanoparticles is called the primary size. It is advantageously between 10 nm and 50 nm, preferably between 10 nm and 30 nm; this favors during the subsequent process steps the formation of an interconnected mesoporous network with electronic and ionic conduction, thanks to the phenomenon of "necking".
This suspension of monodisperse nanoparticles can be purified to remove all potentially troublesome ions. Depending on the degree of purification, it can then be specially treated to form aggregates of a controlled size. More specifically, the formation of aggregates results from the destabilization of the suspension caused by ions. If the suspension has been completely purified it is stable, and ions are added to destabilize it, typically in the form of a salt; these ions are preferably lithium ions (preferably added in the form of LiOH).
If the suspension has not been completely purified, the formation of aggregates can take place by itself spontaneously or by aging. This is easier because it involves fewer purification steps, but it is more difficult to control the size of the aggregates. One of the essential aspects for the manufacture of electrodes according to the invention consists in properly controlling the size of the primary particles of electrode materials and their degree of aggregation.
It is this suspension of nanoparticle aggregates which is then used to deposit, by electrophoresis or by dip-coating, the porous, preferably mesoporous, electrode layers according to the invention.
According to the Applicant's observations, with an average diameter of the nanoparticle aggregates of between 80 nm and 300 nm (preferably between 100 nm and 200 nm), a mesoporous layer having an average diameter of mesopores between 2 nm and 50 nm.
According to the invention, the porous electrode layer can be deposited electrophoretically or by the dip coating process below "dip-coating".
3. Deposition of the layers by electrophoresis
The method according to the invention uses the electrophoresis of nanoparticle suspensions as a technique for depositing porous, preferably mesoporous, electrode layers. The method of depositing electrode layers from a suspension of nanoparticles is known as such (see for example EP 2 774 194 B1). The substrate may be metallic, for example a metallic sheet, or a metallized plastic sheet (ie coated with a layer of metal). One can for example use a sheet of stainless steel with a thickness of 5 μm. The metal sheet can be coated with a layer of noble metal or with a layer of conductive material of ITO type (which has the advantage of also acting as a diffusion barrier). In a particular embodiment, a thin layer of an electrode material is deposited on the metal layer; this deposit must be very thin (typically a few tens of nanometers, and more generally between 10 nm and 100 nm). It can be carried out by a sol-gel process. For example, LiMnO ₄ can be used for a porous LiMn ₂ O ₄ cathode.
In order for the electrophoresis to take place, a counter electrode is placed in the suspension and a voltage is applied between the conductive substrate and said counter electrode.
In an advantageous embodiment, the electrophoretic deposition of the nanoparticle aggregates is carried out by galvanostatic electrodeposition in pulsed mode; high frequency current pulses are applied, this prevents the formation of bubbles on the surface of the electrodes and variations in the electric field in the suspension during deposition. The thickness of the electrode layer thus deposited is advantageously less than 10 μm, preferably less than 8 μm, and is even more preferably between 1 μm and 6 μm.
4. Deposition of a porous electrode layer by dip-coating
Nanoparticle aggregates can be deposited by the dip coating process (called "dip-coating" in English), regardless of the chemical nature of the nanoparticles used. This deposition process is preferred when the nanoparticles used have little or no electrical charge. In order to obtain a layer of a desired thickness, the step of deposition by dip-coating of the nanoparticle aggregates followed by the step of drying the layer obtained are repeated as much as necessary.
Although this succession of steps of coating by dipping / drying is time consuming, the dip-coating deposition process is a simple, safe process, easy to implement, to industrialize and making it possible to obtain a homogeneous final layer and compact.
5. Treatment and properties of the deposited layers
The deposited layers must be dried; drying should not induce cracking. For this reason it is preferred to perform it under controlled humidity and temperature conditions.
The dried layers can be consolidated by a pressing and / or heating step. In a very advantageous embodiment of the invention, this treatment leads to partial coalescence of the primary nanoparticles in the aggregates, and between neighboring aggregates; this phenomenon is called "necking" or "neck training". It is characterized by the partial coalescence of two particles in contact, which remain separate but connected by a neck (constricted); this is illustrated schematically in Figure 2. The lithium ions and the electrons are mobile within these necks and can diffuse from one particle to another without meeting grain boundaries. The nanoparticles are welded together to ensure the conduction of electrons from one particle to another. Thus is formed a three-dimensional network of interconnected particles with high ionic mobility and electronic conduction; this network comprises pores, preferably mesopores.
The temperature required to obtain necking depends on the material; taking into account the diffusive nature of the phenomenon which leads to necking, the duration of the treatment depends on the temperature.
The inventors have found that due to the very large specific surface area of porous electrodes, preferably mesoporous electrodes according to the invention, during their use with a liquid electrolyte, parasitic reactions can occur between the electrodes and the electrolyte; these reactions are at least partially irreversible. In an advantageous embodiment, a very thin dielectric layer (ie an electronic insulator) is applied to the porous electrode layer, preferably a mesoporous one, in order to block these parasitic reactions. This dielectric layer advantageously has an electronic conductivity of less than 10 ' ⁸ S / cm. Advantageously, this deposition is carried out at least on one face of the electrode which forms the interface between the electrode and the electrolyte. This layer can for example be made of alumina, silica, or zirconia. On the cathode, Li ₄ Ti ₅ 0i2 0u or another material which, like Li ₄ Ti ₅ 0i2, has the characteristic of not inserting, at the operating voltages of the cathode, of lithium and of behaving like a electronic insulator.
Alternatively, this dielectric layer may be an ionic conductor, which advantageously has an electronic conductivity of less than 10 ' ⁸ S / cm. This material must be chosen so as not to insert lithium at the operating voltages of the battery, but only to transport it. As such, Li ₃ PO ₄ , Li ₃ BO ₃ , lithium lanthanum zirconium oxide (called “LLZO”), such as Li ₇ La ₃ Zr ₂ 0 ₂ , which have a wide range of potential, can be used in this respect. Operating. On the other hand, lithium lanthanum titanium oxide (abbreviated "LLTO"), such as Li _3x La _2/3 _ _x TiO ₃ , lithium aluminum titanium phosphate (abbreviated "LATP"), lithium aluminum germanium phosphate (abbreviated "LAGP »), Can only be used in contact with the cathodes because their operating potential range is restricted; beyond this range they are likely to insert lithium into their crystallographic structure.
This deposition further improves the performance of lithium ion batteries comprising at least one porous electrode according to the invention. The improvement observed essentially consists of a reduction in faradaic interface reactions with electrolytes. These parasitic reactions are all the more important the higher the temperature; they are the cause of reversible and / or irreversible loss of capacity.
Very advantageously, this deposition is carried out by a technique allowing an enveloping coating (also called "conformal deposition"), i.e. a deposition which faithfully reproduces the atomic topography of the substrate to which it is applied. The technique of ALD (Atomic Layer Deposition), known as such, may be suitable. It can be implemented on the electrodes before and / or after the deposition of the separator particles and before assembly of the cell. The deposition technique by ALD is done layer by layer, by a cyclic process, and makes it possible to produce a coating coating which faithfully reproduces the topography of the substrate; it lines the entire surface of the electrodes. This coating coating typically has a thickness of between 1 nm and 5 nm.
In this variant of deposition of a dielectric nanolayer, it is preferable for the primary diameter D ₅₀ of the particles of electrode material to be at least 10 nm in order to prevent the dielectric layer from blocking the open porosity of the layer. electrode.
The dielectric layer should only be deposited on porous electrodes that do not contain an organic binder. In fact, the deposition by ALD is carried out at a temperature typically between 100 ° C. and 300 ° C. At this temperature, the organic materials forming the binder (for example the polymers contained in the electrodes produced by ink casting tape) risk decomposing and will pollute the ALD reactor. Furthermore, the presence of residual polymers in contact with the particles of electrode active material can prevent the ALD coating from coating all of the particle surfaces, which affects its effectiveness.
For example, an alumina layer with a thickness of about 1.6 nm may be suitable.
In general, the method according to the invention, which necessarily involves a step of electrophoresis deposition of nanoparticles of electrode material (active material), causes the nanoparticles to naturally "weld" together to generate a structure porous, rigid, three-dimensional, without organic binder; this porous layer, preferably mesoporous, is perfectly well suited to the application of an ALD surface treatment which enters the depth of the open porous structure of the layer.
On the porous electrodes, preferably mesoporous, coated or not with a dielectric layer by ALD, it is also possible to deposit a porous layer, preferably mesoporous of nanoparticles of a dielectric material which will serve as a porous separator. This material can in particular be silica, alumina, zirconia. This porous layer, applied between the electrodes will be impregnated by capillarity with a phase carrying lithium ions such as liquid electrolytes in order to produce a battery cell.
It is also possible to deposit a layer of a solid electrolyte which is a conductor of lithium ions and an electron insulator, for example Li ₃ PO ₄ as a porous separator. In one embodiment, a monodisperse colloidal suspension of silica nanoparticles is used (commercially available, for example from the company Alfa Aesar), with a particle size of 20 nm, which is diluted to 20 g / l. This suspension is then destabilized by adding LiOH to modify its ionic charge until aggregates of size approaching 100 nm are obtained. From this colloidal suspension of nanoparticle aggregates, two layers are produced by electrophoresis with a thickness of 1.5 μm each, respectively on the anode and the cathode. These layers are then dried.
6. Special aspects for the preparation of cathodes
If the electrode according to the invention is a cathode, it can be made from a cathode material P chosen from:
oxides LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiMm.sNio.sO ^ υΜη _1ι5 Νίο, 5- _χ Χ _χ 0 ₄ where X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earths such as Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and where 0 <x <0.1, LiMn ₂ . _x M _x O ₄ with M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg or a mixture of these compounds and where 0 <x <0.4, LiFeO _2, LiMn _{1 /} 3Ni ₁ / 3Co _1/3 O _2, LiNi0.8Co0.15AI0.05O3, LiFePO ₄ phosphates, LiMnPO _4, LiCoPO _4, LiNiPO _4, Li ₃ V ₂ (PO _{4) 3;} phosphates of formula LiMM'PO ₄ , with M and M '(M + M') selected from Fe, Mn, Ni, Co, V;
- all the lithiated forms of the following chalcogenides: V ₂ O ₅ , V ₃ O ₈ , TiS ₂ , titanium oxysulfides (TiO _y S _z with z = 2-y and 0.3 <y <1), oxysulfides of tungsten (WO _y S _z with 0.6 <y <3 and 0.1 <z <2), CuS, CuS ₂ , preferably Li _x V ₂ O ₅ with 0 <x <2, Li _x V ₃ O ₈ with 0 <x <1.7, Li _x TiS ₂ with 0 <x <1, titanium and lithium oxysulfides Li _x TiO _y S _z with z = 2-y, 0.3 <y <1, Li _x WO _y S _z , Li _x CuS, Li _x CuS ₂ .
7. Special aspects for the preparation of anodes
If the electrode according to the invention is an anode, it can be made from an anode material P chosen from:
lithiated iron phosphate (of typical formula LiFePO ₄ );
mixed oxynitrides of silicon and tin (of typical formula Si _a Sn _b O _y N _z with a> 0, b> 0, a + b <2, 0 <y <4, 0 <z <3) (also called SiTON ), and in particular the SiSn _{0, 87} Oi, ₂ N _1i72; as well as the oxynitride-carbides of typical formula Si _a Sn _b C _c O _y N _z with a> 0, b> 0, a + b <2, 0 <c <10, 0 <y <24, 0 <z <17;
nitrides of type Si _x N _y (in particular with x = 3 and y = 4), Sn _x N _y (in particular with x = 3 and y = 4), Zn _x N _y (in particular with x = 3 and y = 2), Li ₃ . _x M _x N (with 0 <x <0.5 for M = Co, 0 <x <0.6 for M = Ni, 0 <x <0.3 for M = Cu); If ₃ . _x M _x N ₄ with 0 <x <3.
oxides SnO ₂ , SnO, Li ₂ SnO ₃ , SnSiO ₃ , LixSiO _y (x> = 0 and 2>y> 0), Li ₄ Ti ₅ 0i ₂ , 5ηΒ _Ο , 6Ρθ, 4θ2.9 © t TiO ₂ .
8. Manufacture of batteries using the electrodes according to the invention
Porous electrodes according to the invention may or may not be coated with a dielectric layer, in particular by ALD.
These coated or uncoated electrodes can then be covered with a porous layer acting as a separator so that there is, between each electrode coated or not with a dielectric layer by ALD, a porous layer. In one embodiment, the material used for the manufacture of this porous layer playing the role of separator is chosen from inorganic materials with low melting point, electrical insulation and stable in contact with the electrodes during the hot pressing steps. The more refractory the materials, the more it will be necessary to heat to high temperatures, thus risking modifying the interfaces with the electrode materials, in particular by interdiffusion, which generates parasitic reactions and creates depletion layers whose electrochemical properties differ. from those found in the same material at a greater depth from the interface.
The material used for the manufacture of porous layers acting as a separator is preferably inorganic. In a particular embodiment, the material used for the manufacture of this porous layer playing the role of separator is an electrically insulating material. It can preferably be chosen from AI ₂ O ₃ , SiO ₂ , ZrO ₂ .
Alternatively, the material used for the manufacture of this porous layer acting as a separator can be an ionic conductive material such as a solid electrolyte. According to the invention, the solid electrolyte material used for the manufacture of a porous layer acting as a separator can be chosen in particular from:
o garnets of formula Li _d A ¹ x A ² y (TO ₄ ) _z where
A ¹ represents a cation of oxidation state + II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and or
A ² represents a cation of oxidation state + III, preferably Al, Fe, Cr, Ga, Ti, La; and where (TO ₄ ) represents an anion in which T is an atom of degree of oxidation + IV, located at the center of a tetrahedron formed by the oxygen atoms, and in which TO ₄ advantageously represents the silicate anion or zirconate, knowing that all or part of the elements T of an oxidation state + IV can be replaced by atoms of an oxidation state + III or + V, such as Al, Fe, As, V, Nb, In, Ta;
knowing that: d is between 2 and 10, preferably between 3 and 9, and even more preferably between 4 and 8; x is between 2.6 and 3.4 (preferably between 2.8 and 3.2); y is between 1.7 and 2.3 (preferably between 1.9 and 2.1) and z is between 2.9 and 3.1;
o garnets, preferably chosen from: Li ₇ La ₃ Zr ₂ 0i ₂ ; Li ₆ La ₂ BaTa ₂ 0i ₂ ; Li5,5La ₃ Nb _1i7 5lno. ₂ 50i ₂ ; Li ₅ La ₃ M ₂ 0i ₂ with M = Nb or Ta or a mixture of the two compounds; the Li ₇ . _x Ba _x La ₃ . _x M ₂ 0i ₂ with 0 <x <1 and M = Nb or Ta or a mixture of the two compounds; the Li ₇ . _x La ₃ Zr ₂ . _x M _x Oi ₂ with 0 <x <2 and M = Al, Ga or Ta or a mixture of two or three of these compounds;
o lithiated phosphates, preferably chosen from: lithiated phosphates of the NaSICON type, Li ₃ PO ₄ ; LiPO ₃ ; Li ₃ Alo, ₄ Sc ₁₆ (P0 ₄ ) ₃ called “LASP”; Li ₃ (Sc _{2. x} M _x ) (PO ₄ ) ₃ with M = AI or Y and 0 <x <1; Li _{1 + x} M _x (Sc) ₂ . _x (PO ₄ ) ₃ with M = Al, Y, Ga or a mixture of the three compounds and 0 <x <0.8; Li _{1 + x} M _x (Ga _{1. y} Sc _y ) ₂ . _x (PO ₄ ) ₃ with 0 <x <0.8; 0 <y <1 and M = Al or Y or a mixture of the two compounds; Li _{1 + x} M _x (Ga) ₂ . _x (PO ₄ ) ₃ with M = Al, Y or a mixture of the two compounds and 0 <x <0.8; Li _{1 + x} Al _x Ti ₂ . _x (PO ₄ ) ₃ with 0 <x <1 called "LATP"; or Li _{1 + x} Al _x Ge ₂ . _X (PO ₄ ) ₃ with 0 <x <1 called "LAGP"; or Liux + zMxtGevyTiyl ^ xSizPs-zO ^ with 0 <x <0.8 and 0 <y <1.0 and 0 <z <0.6 and M = Al, Ga or Y or a mixture of two or three of these compounds; Li _{3 + y} (Sc _{2. x} M _x ) Q _y P _3. yOi ₂ with M = Al and / or Y and Q = Si and / or Se, 0 <x <0.8 and 0 <y <1 ; or Li _{1 + x + y} M _x Sc ₂ . _x Q _y P ₃ .yOi ₂ with M = Al, Y, Ga or a mixture of the three compounds and Q = Si and / or Se, 0 <x <0.8 and 0 <y <1; or the U _{1 + x +} y _{+ z} M _x (Ga ₁ .ySCy) ₂ . _x QzP ₃ .zOi ₂ with 0 <x <0.8.0 <y <1, 0 <z <0.6 with M = Al or Y or a mixture of the two compounds and Q = Si and / or Se; or Li _{1 + X} M ³ _X M ₂ . _x P ₃ 0i ₂ with 0 <x <1 and M ³ = Cr and / or V, M = Sc, Sn, Zr, Hf, Se or Si, or a mixture of these compounds;
o the lithiated borates, preferably chosen from: Li ₃ (Sc _{2. x} M _x ) (BO ₃ ) ₃ with M = AI or Y and 0 <x <1; Li _{1 + x} M _x (Sc) ₂ . _x (BO ₃ ) ₃ with M = Al, Y, Ga or a mixture of the three compounds and 0 <x <0.8; Lh + xMxtGavySCy ^ .xtBOsjs with 0 <x <0.8.0 <y <1 and M = Al or Y; Li _{1 + x} M _x (Ga) ₂ . _x (BO ₃ ) ₃ with M = Al, Y or a mixture of the two compounds and 0 <x <0.8; Li ₃ BO ₃ , Li ₃ BO ₃ -Li ₂ SO ₄ , Li ₃ BO ₃ -Li ₂ SiO ₄ , Li ₃ BO ₃ Li ₂ SiO ₄ -Li ₂ SO ₄ ;
o oxynitrides, preferably chosen from Li ₃ PO ₄ . _x N _{2x / 3} , Li ₄ SiO ₄ . _x N _{2x / 3} , Li ₄ GeO ₄ . _x N _{2x / 3} with 0 <x <4 or Li ₃ BO ₃ . _x N _{2x / 3} with 0 <x <3;
o the lithiated compounds based on lithium oxynitride and phosphorus, called “LiPON”, in the form of Li _x PO _y N _z with x ~ 2.8 and 2y + 3z ~ 7.8 and 0.16 <z < 0.4, and in particular Li ₂ , ₉ PO ₃ , ₃ N ₀ , ₄ 6, but also the compounds Li _w PO _x N _y S _z with 2x + 3y + 2z = 5 = w or the compounds Li _w PO _x N _y S _z with 3.2 <x <3.8, 0.13 <y <0.4, 0 <z <0.2, 2.9 <w <3.3 or the compounds in the form of LitP _x Al _y O _w with _u NvS 5x + 3y = 5, 2u + 3v + 2w + t = 5, 2.9 <t <3.3, 0.84 <x <0.94, 0.094 <y <0, 26, 3.2 <u <3.8,
0.13 <v <0.46, 0 <w <0.2;
o materials based on lithium oxynitrides of phosphorus or boron, called respectively "LiPON" and "LIBON", which can also contain silicon, sulfur, zirconium, aluminum, or a combination of aluminum, boron, sulfur and / or silicon, and boron for materials based on phosphorus lithium oxynitrides;
o the lithiated compounds based on lithium oxynitride, phosphorus and silicon called "LiSiPON", and in particular Lh gSio ^ ePi oOi, i Ni. _o ;
o lithium oxynitrides of LiBON, LiBSO, LiSiPON, LiSON, thioLiSiCON, LiPONB types (or B, P and S represent boron, phosphorus and sulfur respectively);
o LiBSO type lithium oxynitrides such as (1-x) LiBO ₂ - xLi ₂ SO ₄ with 0.4 <x <0.8;
o lithiated oxides, preferably chosen from Li ₇ La ₃ Zr ₂ 0i ₂ or Li _{5 + x} La ₃ (Zr _x , A _{2. x} ) Oi ₂ with A = Sc, Y, Al, Ga and 1, 4 <x <2 or the Li ₀ , ₃ 5La ₀ , 55TiO ₃ or the Li _3x La _2/3 . _x TiO ₃ with 0 <x <0.16 (LLTO);
o silicates, preferably chosen from Li ₂ Si ₂ O ₅ , Li ₂ SiO ₃ , Li ₂ Si ₂ O ₆ , LiAISiO ₄ , Li ₄ SiO ₄ , LiAISi ₂ O ₆ ;
o solid electrolytes of anti-perovskite type chosen from: Li ₃ OA with A halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these; Li ^ M ^ OA with 0 <x <3, M a divalent metal, preferably at least one of the elements chosen from Mg, Ca, Ba, Sr or a mixture of two or three or four of these elements, A halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these elements; Li ^ M ^ OA with 0 <x <3, M ³ a trivalent metal, A a halide or a mixture of halides, preferably at least one of the elements chosen from F, Cl, Br, I or a mixture of two or three or four of these; or LICOX _z Y _{(i. Z),} with X and Y of the halide as mentioned above in relation to A, and 0 <z <1, where the compounds The _0, 5iLi _{0, 34} Ti _{2, 94,} Li ₃ , ₄ V ₀ , ₄ Ge ₀ , 6O ₄ , Li ₂ O-Nb ₂ O ₅ , LiAIGaSPO ₄ ;
o formulations based on Li ₂ CO ₃ , B ₂ O ₃ , Li ₂ O, AI (PO ₃ ) ₃ LiF, P ₂ S ₃ , Li ₂ S, Li ₃ N, Lii ₄ Zn (GeO ₄ ) ₄ , Li _3i 6Geo, 6Vo, ₄ 0 ₄ , LiTi ₂ (PO ₄ ) ₃ , Li ₃₂ 5Geo, ₂ 5Po, 25S ₄ , Lii, ₃ Alo, ₃ Tii _ι7 (ΡΟ ₄ ) ₃ , Lii _{+ X} AI _X M ₂ . _X (PO ₄ ) ₃ (where M = Ge, Ti, and / or Hf, and where 0 <x <1), Li _{1 + x + y} Al _x Ti ₂ . _x If _y P ₃ . _y Oi ₂ (where 0 <x <1 and 0 <y <1).
Advantageously, this porous layer playing the role of separator can be deposited, in the same way as the electrode layers on their support, electrophoretically or by dip-coating from a suspension of nanoparticles.
Preferably, the electrodes according to the invention are covered with a porous layer acting as a separator and then stacked so that these porous layers are in contact.
This stack comprising an alternating succession of cathode and anode in thin layers covered with a porous layer is then hot pressed under vacuum, it being understood that at least one cathode or anode according to the invention is used in this stack. The pressure and the temperature employed during the hot pressing of the stack allowing the realization of the assembly depend in particular on the nature of the materials composing the stack and on the size of the primary particles used to make the electrodes and the porous layer playing the role of separator.
Advantageously, the stack is placed under a pressure of between 0.5 MPa and 3 MPa, preferably around 1.5 MPa and is then dried under vacuum. This maintains the stack during drying. The press plates are then heated to a set temperature, preferably 450 ° C with a speed of a few degrees ° C per second. At 450 ° C, the stack is then thermo-compressed under a pressure allowing the assembly of the stack, preferably 45 MPa for 1 minute, then the system is cooled to room temperature.
Once the assembly has been carried out, a rigid, multilayer system consisting of one or more assembled cells is obtained.
This assembly is then impregnated with a phase carrying lithium ions, preferably in an electrolytic solution.
9. Impregnation of the assembled battery, and more particularly of the electrode layers and of the battery separator
Once the assembly of a stack constituting a battery by hot pressing is complete, it can be impregnated with a phase carrying lithium ions. This phase can be a solution formed by a lithium salt dissolved in an organic solvent or a mixture of organic solvents, and / or dissolved in a polymer containing at least one lithium salt, and / or dissolved in an ionic liquid (ie a molten lithium salt) containing at least one lithium salt. This phase can also be a solution formed from a mixture of these components. The inventors have found that the porous electrodes according to the invention are capable of absorbing a liquid phase by simple capillarity. This completely unexpected effect is specific to the deposition of porous electrodes, preferably mesoporous according to the invention; it is particularly favored when the mean diameter D ₅₀ of the pores is between 2 nm and 80 nm, preferably between 2 nm and 50 nm, preferably between 6 nm and 30 nm, preferably between 8 nm and 20 nm. Its pores are impregnated by the phase carrying lithium ions, ie by an electrolyte, such as an ionic liquid containing lithium salts, possibly diluted in an organic solvent or a mixture of organic solvents containing a lithium salt which may be different from that dissolved in the ionic liquid.
The impregnation can be done either for the anode, or for the cathode, or even for both.
In an advantageous embodiment of the invention, the porous, preferably mesoporous, electrode has a porosity greater than 30% by volume, pores with an average diameter D ₅₀ less than 80 nm, preferably less than 50 nm, a diameter particle primary less than 30 nm. Its thickness is advantageously less than 10 μm, and preferably between 2.5 μm and 4.5 μm, so as to reduce the final thickness of the battery. It is free of binder.
Advantageously, the porous thin layer electrode has a porosity of between 35% and 50% by volume, and even more preferably between 40% and 50% by volume; it is preferably mesoporous.
In an advantageous embodiment of the invention, the porous layer playing the role of separator, has a porosity greater than 30% by volume, pores with an average diameter D ₅₀ less than 50 nm. This porous layer acting as a separator is capable of absorbing a liquid phase such as a phase carrying lithium ions by simple capillarity in its pores. This effect is particularly favored when the mean diameter D ₅₀ of the mesopores is between 2 nm and 50 nm, preferably between 6 nm and 30 nm, preferably between 8 nm and 20 nm. Its thickness is advantageously less than 10 μm. It is free of binder. Advantageously, the porosity of the porous layer acting as a separator is between 35% and 50% by volume, and even more preferably between 40% and 50% by volume; it is preferably mesoporous.
The liquid “nanoconfined” or “nanopiégé” in the porosities, preferably in the mesoporosities, can no longer come out. It is linked by a phenomenon called here "absorption in the mesoporous structure" (which does not seem to have been described in the literature in the context of lithium ion batteries) and can no longer leave even when the cell is placed under vacuum. The battery is then considered to be almost solid.
The phase carrying lithium ions can be an electrolytic solution comprising PYR14TFSI and LiTFSI; these abbreviations will be defined below.
After impregnation with a phase carrying lithium ions, the assembly of the stack constituting a battery is dried, preferably, by an N ₂ blade leading to the production of a lithium ion battery comprising at least one, or even several electrochemical cells, each comprising electrodes according to the invention.
We describe here the production of a battery with a separator based on a solid electrolyte, based on Li ₃ AI ₀ , ₄ Sc ₁₆ (PO ₄ ) ₃ . The mesoporous cathode layer (LiMn ₂ O ₄ ), coated with a mesoporous layer of Li ₃ AI ₀₄ Sc ₁₆ (PO ₄ ) ₃ , and the mesoporous anode layer (Li ₄ Ti ₅ 0i ₂ ) are also produced. coated with a mesoporous layer of Li ₃ Alo, ₄ Sci e (PO ₄ ) ₃ .
The suspension of nanoparticles of electrolyte material is prepared hydrothermally, which leads directly to nanoparticles of good crystallinity. The electrolyte layer is deposited by electrophoresis or by dip-coating on the cathode layer and / or on the anode layer, described above, previously or not coated with a dielectric layer deposited by ALD. The assembly is done by hot pressing, under an inert atmosphere, at a temperature between 300 ° C and 500 ° C, preferably between 350 ° C and 450 ° C and a pressure between 50 MPa and 100 MPa, for example at 350 ° C and 100 MPa.
Then, this cell, which is completely solid and rigid, and which contains no organic material, is impregnated by immersion in a liquid electrolyte conductive of lithium ions. Due to the open porosity and the small size of the porosities (less than 50 nm), the impregnation throughout the cell (electrode and separator made of Li ₃ Alo, ₄ Sc ₁₆ (P0 ₄ ) ₃ mesoporous) done by capillary action. The liquid electrolyte may for example be LiPF ₆ or LiBF ₄ dissolved in an aprotic solvent, or an ionic liquid containing lithium salts. Ionic liquids and organic electrolytes can also be mixed. One can for example mix at 50% by mass the LiPF ₆ dissolved in EC / DMC with an ionic liquid containing lithium salts of LiTFSI type: PYR14TFSI 1: 9 mol. It is also possible to make mixtures of ionic liquids which can operate at low temperature, for example the LiTFSI: PYR13FSI: PYR14TFSI mixture (2: 9: 9 mol ratio).
EC is the common abbreviation for ethylene carbonate (CAS No: 96-49-1). DMC is the common abbreviation for dimethyl carbonate (CAS No: 616-38-6). LITFSI is the common abbreviation for lithium bis-trifluoromethanesulfonimide (CAS No: 90076-65-6). PYR13FSI is the common abbreviation for N-Propyl-N-Methylpyrrolidinium bis (fluorosulfonyl) imide. PYR14TFSI is the common abbreviation for 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide.
We describe here another example of manufacturing a lithium ion battery according to the invention. This process includes the steps of:
(1) Supply of a colloidal suspension comprising nanoparticles of at least one cathode material of average primary diameter D ₅₀ less than or equal to 50 nm;
(2) Supply of a colloidal suspension comprising nanoparticles of at least one anode material with an average primary diameter D ₅₀ less than or equal to 50 nm;
(3) Supply of at least two flat, preferably metallic, conductive substrates, said conductive substrates being able to serve as battery current collectors, (4) Deposit of at least one thin layer of cathode, respectively of anode, by dip-coating or by electrophoresis, preferably by galvanostatic electrodeposition by pulsed currents, from said suspension of nanoparticles of material obtained in step (1), respectively in step (2), on said substrate obtained in step (3), (5) Drying of the layer thus obtained in step (4), (6) Optionally, deposition by ALD of a layer of an electrically insulating material on and inside the pores of the cathode and / or anode layer obtained in step (5), (7) Electrophoresis deposition of a film of an electrically insulating material or a mesoporous ionic conductive material from a colloidal suspension nanoparticles of this material ag governed by an average primary diameter D ₅₀ less than or equal to 50 nm and an average diameter D ₅₀ of approximately 100 nm on the cathode layer, respectively anode layer obtained in step (5) and / or step (6 ), (8) Drying of the layer thus obtained in step (7), (9) Stack comprising an alternating succession of cathode and anode layers in thin layers, offset laterally, (10) Hot pressing of the layers anode and cathode obtained in step (9) so as to juxtapose the films obtained in step (8) present on the anode and cathode layers, (11) Impregnation of the structure obtained in step (10) by a phase carrying lithium ions leading to the production of an impregnated structure, preferably a cell.
A lithium ion battery cell of very high power density is thus obtained. The liquid “nanoconfined” or “nanopiégé” in the mesoporosities can no longer emerge as indicated above; the battery is then considered to be almost solid.
Here we describe the manufacture of a lithium ion battery which is well suited for use at low temperatures. As noted above, the series resistance of a battery increases as the temperature drops. For a fully solid lithium ion battery (as described for example in patent applications WO 2013/064 781 or WO 2013/064 779), the ionic conductivity of the electrolyte decreases by approximately half when the temperature drops by 7 ° C. To solve this problem, a battery according to the invention is used with mesoporous electrodes, a porous layer, preferably a mesoporous layer acting as a separator, which is impregnated with an electrolyte which is preferably an ionic liquid comprising lithium ions; the ionic liquid can be diluted in a suitable organic solvent. One can for example use a mixture at 50% by mass of LiPF ₆ in EC / DMC with LiTFSI: PYR14TFSI 1: 9 mol. Impregnation takes place after assembly of a stack comprising an alternating succession of cathode and anode layers in thin layers covered with a porous layer acting as a separator, as has just been described, after the step (11).
By way of example, the deposition of the electrodes, either of the anode or of the cathode, or, what is preferred, of both, can be done with aggregated nanoparticles with an average diameter D ₅₀ of approximately 100 nm, obtained from primary nanoparticles with an average diameter D ₅₀ less than or equal to 50 nm; each electrode may have a thickness of about 4 µm.
The method according to the invention can be used for the manufacture of porous or mesoporous electrodes in a thin layer, in electronic, electrical or electrotechnical devices, and preferably in devices selected from the group formed by: batteries, capacitors, supercapacitors, capacitors, resistors, inductors, transistors, photovoltaic cells.
10. Encapsulation
The battery must then be encapsulated by an appropriate method to ensure its protection from the atmosphere. The encapsulation system comprises at least one layer, and preferably represents a stack of several layers. If the encapsulation system consists of a single layer, it must be deposited by, ALD or be made of parylene and / or polyimide. These encapsulation layers must be chemically stable, withstand high temperatures and be impermeable to the atmosphere (barrier layer). One of the methods described in patent applications WO 2017/115,032, WO 2016/001584, W02016 / 001588 or WO 2014/131997 can be used. Preferably, said at least one encapsulation layer covers four of the six faces of said battery, the other two faces of the battery being coated with the terminations.
Advantageously, the first layer is a polymeric layer, preferably based on polyimide and / or parylene. It can be deposited under vacuum, by a chemical vapor deposition (CVD) technique. This first encapsulation layer is advantageously obtained from the condensation of gaseous monomers deposited by a chemical vapor deposition (CVD) technique on the surfaces, which allows a conformai and uniform covering of all of the accessible stack surfaces. It makes it possible to follow the variations in volume of the battery during its operation and facilitates the clean cutting of the batteries due to its elastic properties. The thickness of this first encapsulation layer is between 2 μm and 10 μm, preferably between 2 μm and 5 μm and even more preferably around 3 μm. It makes it possible to cover all of the accessible surfaces of the stack, to close all of the pores of these accessible surfaces and to standardize the chemical nature of the substrate. The encapsulation can thus be carried out directly on the stacks, the coating being able to penetrate into all of the available cavities. It is recalled here that thanks to the nanoconfinement of the conductive phase carrying lithium ions in the porosities of the electrodes according to the invention and / or of the electrolyte, the battery can undergo treatments under vacuum.
In one embodiment, a first layer of parylene is deposited, 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. Parylene (also called polyparaxylylene or poly (p-xylylene)) is a dielectric, transparent, semi-crystalline material which has high thermodynamic stability, excellent resistance to solvents and very low permeability.
This parylene layer protects the sensitive elements of the battery from their environment. This protection is increased when this first encapsulation layer is made from parylene N. However, the inventors have observed that this first layer, when it is based on parylene, does not have sufficient stability in the presence of oxygen. . When this first layer is based on polyimide, it does not have a sufficient seal, especially in the presence of water. For these reasons, a second layer is deposited which coats the first layer.
Advantageously, a second layer composed of an electrically insulating material, preferably inorganic, can be deposited by a conformai deposition technique, such as the deposition of atomic layers (ALD) on this first layer. Thus a conformai covering is obtained of all the accessible surfaces of the stack covered with a layer of parylene and / or polyimide; this second 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 different zones of different chemical natures will have an inhomogeneous growth, which can cause a loss of integrity of this second protective layer.
The ALD deposition techniques are particularly well suited for covering surfaces with high roughness in a completely waterproof and conforming manner. They make it possible to produce conformal layers, free of defects, such as holes (so-called “pinhole free” layers, free of holes) and represent very good barriers. Their WVTR coefficient is extremely low. The WVTR (water vapor transmission rate) coefficient makes it possible to assess the water vapor permeance of the encapsulation system. The lower the WVTR coefficient, the more waterproof the encapsulation system. For example, a layer of AI ₂ O ₃ 100 nm thick deposited by ALD has a water vapor permeation of 0.00034 g / m ² .d. The second layer may be made of ceramic material, glassy material or glass-ceramic material, for example in the form of oxide, of the AI ₂ O _{3 type} , of nitride, of phosphates, of oxynitride, or of siloxane. This second encapsulation layer 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 of the order of fifty nanometers. A conformai deposition technique is preferred, such as atomic layer deposition (ALD).
This second layer deposited by ALD on the first polymer layer makes it possible on the one hand, to ensure the tightness of the structure, ie to prevent the migration of water inside the structure and on the other hand to protect the first layer of parylene and / or polyimide from the atmosphere, in particular from air and humidity, from thermal exposure in order to avoid its degradation. This second layer improves the life of the encapsulated battery.
However, these layers deposited by ALD are very fragile mechanically and require a rigid support surface to ensure their protective role. The deposition of a fragile layer on a flexible surface would lead to the formation of cracks, causing a loss of integrity of this protective layer.
Advantageously, a third encapsulation layer is deposited on the second encapsulation layer to increase the protection of the battery cells from their external environment. Typically, this third layer is made of polymer, for example silicone (deposited for example by impregnation or by chemical vapor deposition assisted by plasma from hexamethyldisiloxane (HMDSO)), or in epoxy resin, or in polyimide, or in parylene.
In addition, the encapsulation system can comprise an alternating succession of layers of parylene and / or polyimide, preferably approximately 3 μm thick, and of layers composed of an electrically insulating material such as deposited inorganic layers. conformally by ALD as previously described to create a multi-layer encapsulation system. In order to improve the performance of the encapsulation, the encapsulation system can advantageously comprise a first layer of parylene and / or polyimide, preferably about 3 μm thick, a second layer composed of a material electrically insulating, preferably an inorganic layer, conformally deposited by ALD on the first layer, a third layer of parylene and / or polyimide, preferably about 3 μm thick deposited on the second layer and a fourth layer composed of an electrically insulating material conformally deposited by ALD on the third layer.
Advantageously, a last encapsulation layer is deposited on this alternating succession of parylene or polyimide layers, preferably about 3 μm thick and inorganic layers deposited in a conformal manner by ALD, to increase the protection of the battery cells. from their external environment and protect them from mechanical damage. This last encapsulation layer has a thickness of about 10-15 µm. Typically, this last layer is made of polymer, for example silicone (deposited for example by dipping or by chemical vapor deposition assisted by plasma from hexamethyldisiloxane (HMDSO)), or epoxy resin, or polyimide, or parylene. For example, it is possible to deposit by injection of a layer of silicone (typical thickness around 15 μm) 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 soldering on electronic cards without the appearance of glass transitions.
Advantageously, the encapsulation of the battery is carried out on four of the six faces of the stack. The encapsulation layers surround the periphery of the stack, the rest of the protection against the atmosphere being provided by the layers obtained by the terminations.
After the battery encapsulation step, terminations are added to establish the electrical contacts necessary for the proper functioning of the battery.
To carry out the terminations, the encapsulated stack is cut along cutting planes making it possible to obtain unitary battery components, with the baring on each of the cutting planes of the anodic and cathodic connections of the battery, so that the encapsulation system covers four of the six faces of said battery, preferably continuously, so that the system can be assembled without welding, the other two faces of the battery being coated subsequently with the terminations. Advantageously, the battery comprises terminations at the level where the cathode current collectors, respectively anodic, are apparent. Preferably, the anode connections and the cathode connections are on the opposite sides of the stack. A termination system is placed on and around these connections. The connections can be metallized using plasma deposition techniques known to those skilled in the art, preferably by ALD and / or by immersion in a conductive epoxy resin loaded with silver and / or a tin bath in fusion. Preferably, the terminations consist of a stack of layers successively comprising a first thin layer of electronically conductive covering, preferably metallic, deposited by ALD, a second layer of silver-loaded epoxy resin deposited on the first layer and a third layer based on tin deposited on the second layer. The first conductive layer deposited by ALD is used to protect the section of the battery from humidity. This first conductive layer deposited by ALD is optional. It increases the calendar life of the battery by reducing the WVTR at the termination level. This first thin covering layer may in particular be metallic or based on metallic nitride. The second layer of epoxy resin loaded with silver, provides "flexibility" to the connectors without breaking the electrical contact when the electrical circuit is subjected to thermal and / or vibratory stresses.
The third layer of tin-based metallization is used to ensure the solderability of the component.
In another embodiment, this third layer can be composed of two layers of different materials. A first layer coming into contact with the epoxy resin layer loaded with silver. This layer is made of nickel and is produced by electrolytic deposition. The nickel layer acts as a thermal barrier and protects the rest of the component from diffusion during the reflow assembly steps. The last layer, deposited on the nickel layer, is also a metallization layer, preferably made of tin to make the interface compatible with reflow assemblies. This layer of tin can be deposited either by soaking in a molten tin bath or by electrodeposition; these techniques are known as such.
For some assemblies on copper tracks by micro-wiring, it may be necessary to have a last layer of copper metallization. Such a layer can be produced by electrodeposition in place of tin.
In another embodiment, the terminations can consist of a stack of layers successively comprising a layer of epoxy resin loaded with silver and a second layer based on tin or nickel deposited on the first layer.
In another embodiment, the terminations can consist of a stack of layers successively comprising a layer of conductive polymer such as a layer of epoxy resin loaded with silver, a second layer based on nickel deposited on the first layer and a third layer based on tin or copper.
In a preferred embodiment, the terminations can consist of different layers which are respectively, without limitation, a layer of conductive polymer such as an epoxy resin loaded with silver, a layer of nickel and a layer of tin.
The terminations allow the alternating positive and negative electrical connections to be taken up at each end of the battery. These terminations allow electrical connections to be made in parallel between the various battery cells. For this, only the cathode connections exit on one end, and the anode connections are available on the other ends. Advantageously, the anodic and cathodic connections are on the opposite sides of the stack
Advantageously, after step (11) of the process for manufacturing a lithium ion battery according to the invention:
successively, alternately, on the impregnated structure:
at least a first layer of parylene and / or polyimide on said battery, at least a second layer composed of an electrically insulating material by ALD (Atomic Layer Deposition) on said first layer of parylene and / or polyimide, and on the alternating succession of at least a first and at least a second layer is deposited a layer for protecting the battery against mechanical damage to the battery, preferably silicone, epoxy resin, or polyimide or parylene, thus forming a battery encapsulation system, the impregnated structure thus encapsulated is cut along two section planes to expose anode and cathode connections of the battery on each of the sectional planes, so that the system encapsulation covers four of the six faces of said battery, preferably continuously, so as to obtain an elementary battery, successive removal ment, on and around, of these anodic and cathodic connections:
an optional first electronically conductive layer, preferably deposited by ALD, a second layer based on silver-charged epoxy resin, deposited on the first electronically conductive layer, and a third layer based on nickel, deposited on the second layer , and a fourth layer based on tin or copper, deposited on the third layer.
Examples
Example 1: Production of a mesoporous cathode based on LiMn ₂ O ₄ :
A suspension of LiMn ₂ O ₄ nanoparticles was prepared by hydrothermal synthesis: 14.85 g of LiOH, H ₂ O were dissolved in 500 ml of water. 43.1 g of KMnO ₄ were added to this solution and this liquid phase was poured into an autoclave. With stirring, 28 ml of isobutyraldehyde and water were added until a total volume of 3.54 I was reached. The autoclave was then heated to 180 ° C. and kept at this temperature for 6 hours. After slow cooling, a black precipitate obtained in suspension in the solvent was obtained. This precipitate was subjected to a succession of centrifugation steps redispersion in water, until an aggregated suspension was obtained with a conductivity of approximately 300 pS / cm and a zeta potential of -30mV. The size of the primary particles was very homogeneous (monodisperse), of the order of 10 nm to 20 nm, and the aggregates had a size of between 100 nm and 200 nm. The product was characterized by X-ray diffraction and electron microscopy.
These aggregates were deposited by electrophoresis on strips of stainless steel (316L) with a thickness of 5 μm, in an aqueous medium, by applying pulsed currents of 0.6 A at the peak and 0.2 A on average; the applied voltage was around 4 to 6 V for 400 s. There was thus obtained a deposit about 4 μm thick. It was dried in a temperature and humidity controlled oven to prevent the formation of cracks on drying.
It was consolidated at 600 ° C for 1 h in air in order to weld the nanoparticles together, to improve adhesion to the substrate and to perfect the recrystallization of LiMn ₂ O ₄ . The layer has an open porosity of approximately 45% by volume with pores of a size between 10 nm and 20 nm (see below, example 5).
In a variant of this process, a monodisperse colloidal suspension with a particle size between 20 nm and 30 nm was obtained, which was stable, with a zeta potential of the order of 55 mV. In order to obtain aggregates of defined size, a solution of LiOH was added to destabilize the suspension, until aggregates of size of the order of 100 nm were obtained; the zeta potential of this suspension was then 35 mV, and its conductivity greater than several hundred pS / cm. From this colloidal suspension, a layer 4 μm thick was deposited by electrophoresis on a sheet of stainless steel (316L) 5 μm thick. The distance between the electrode and the counter electrodes was of the order of 1 cm, the current density was of the order of 6 mA / cm ² . The duration of the current pulses was 5 ms, and the rest time between pulses of 1 ms. Drying and consolidation were carried out as described above.
Note that in this example the colloidal suspension naturally contains aggregates, due to the residual ionic charge. If the purification is pushed further, by more centrifugation steps and / or ultrafiltration techniques, a stable monodisperse suspension is obtained with a conductivity less than 100 pS / cm. This suspension does not contain any aggregates, and in order for it to be used for the electrophoresis step, it must be destabilized by adding LiOH.
Example 2: Production of a Mesoporous Cathode Based on LiCoO ₂
A suspension of crystalline nanoparticles of LiCoO ₂ was prepared by hydrothermal synthesis. For 100 ml of suspension, the reaction mixture was produced by adding 20 ml of a 0.5M aqueous solution of cobalt nitrate hexahydrate added with stirring to 20 ml of a 3M solution of lithium hydroxide monohydrate followed of a dropwise addition of 20 ml of 50% H ₂ O ₂ . The reaction mixture was placed in an autoclave at 200 ° C for 1 hour; the pressure in the autoclave reached about 15 bars.
A black precipitate was obtained, suspended in the solvent. This precipitate was subjected to a succession of centrifugation steps - redispersion in water, until a suspension with a conductivity of about 200 pS / cm and a zeta potential of -30mV was obtained. The size of the primary particles was in the range of 10 nm to 20 nm and the aggregates were between 100 nm and 200 nm. The product was characterized by X-ray diffraction and electron microscopy.
These aggregates were deposited by electrophoresis on stainless steel strips with a thickness of 5 μm, in an aqueous medium, by applying pulsed currents of 0.6 A at the peak and 0.2 A on average; the applied voltage was of the order of 4 to 6 V for 400 s. There was thus obtained a deposit of approximately 4 μm in thickness. It was consolidated at 600 ° C for 1 h in air in order to weld the nanoparticles together, to improve adhesion to the substrate and to perfect the recrystallization of LiCoO ₂ .
Example 3: Production of a Mesoporous Anode Based on Li ₄ Ti ₅ 0i ₂
A suspension of nanoparticles of Li ₄ Ti ₅ 0i _{2 was} prepared by glycothermal synthesis: 190 ml of 1,4-butanediol were poured into a beaker, and 4.25 g of lithium acetate was added with stirring. The solution was kept stirring until the acetate was completely dissolved. 16.9 g of titanium butoxide were removed under an inert atmosphere and introduced into the acetate solution. The solution was then stirred for a few minutes before being transferred to an autoclave previously filled with an additional 60 ml of butanediol. The autoclave was then closed and purged with nitrogen for at least 10 minutes. The autoclave was then heated to 300 ° C at a rate of 3 ° C / min and kept at this temperature for 2 hours, with stirring. At the end, it was allowed to cool, still with stirring.
A white precipitate suspended in the solvent was obtained. This precipitate was subjected to a succession of centrifugation steps - redispersion in ethanol to obtain a pure colloidal suspension, with low ionic conductivity. It included aggregates of about 150 nm made up of 10 nm primary particles. The zeta potential was around -45 mV. The product was characterized by X-ray diffraction and electron microscopy. Figure 1 (a) shows a diffractogram, Figure 1 (b) a photograph obtained by electron microscopy with primary particle transmission.
These aggregates were deposited by electrophoresis on stainless steel strips with a thickness of 5 μm, in an aqueous medium, by applying pulsed currents of 0.6 A at the peak and 0.2 A on average; the applied voltage was of the order of 3 to 5 V for 500 s. There was thus obtained a deposit of approximately 4 μm in thickness. It was consolidated by an RTA annealing at 40% power for 1 s under nitrogen in order to weld the nanoparticles together, to improve adhesion to the substrate and to perfect the recrystallization of Li ₄ Ti ₅ 0i2.
Example 4: Preparation of an ALD coating on the mesoporous electrodes (case of an alumina deposit on a cathode)
A thin layer of alumina was deposited in an ALD P300B reactor (supplier: Picosun), under a 2 mbar argon pressure at 180 ° C. Argon is used here both as a carrier gas and for purging. Before each deposit, a drying time of 3 hours was applied. The precursors used were water and TMA (trimethylaluminium). A deposit cycle consisted of the following steps:
TMA injection for 200 ms
Room purge with Ar for 6 seconds
Water injection for 50 ms
Chamber purge with Ar for 6 second cycles are applied to achieve a coating thickness of 1.6 nm. After these various cycles, vacuum drying at 120 ° C for 12 hours was applied to remove the reagent residues on the surface.
Example 5: Determination of the specific surface and the pore volume
The specific surface was determined by the BET technique (Brunauer - Emmett - Teller), known to those skilled in the art, on a layer of LiMn ₂ O ₄ (abbreviated here "LMO") obtained by a process similar to that described in Example 1 above. The samples were annealed deposits of LMO with a thickness of 2 μm deposited on each of the two faces of a stainless steel sheet (thickness 5 μm), with a grammage of 0.6 mg / cm ² per face (ie 1 , 2 mg / cm ² on both sides). Two sheets of 5 X 10 cm were cut by laser, rolled up one on the other, and inserted in the glass cell of the BET device. The adsorbent gas used for the analysis was N ₂ . The results are as follows:
Total mass of the sample (sheet + deposit): 0.512 g Deposit mass (m) 0.120 g Deposit mass after 5 h under vacuum at 150 ° C 0,117g BET specific surface (S) 43.80 m ² / g Pore volume (V) 0,2016 cm ³ / g Pore diameter (D = 4V / A) 20 nm
The BET method makes it possible to characterize only the open porosity of diameter less than 50 nm (the pore diameter is calculated by considering that the pores are cylindrical). The estimation of the open porosity of dimension greater than 50 nm would require the use of other methods (intrusion of mercury). It can be noted, however, that this limit diameter corresponds to the maximum porosity measured in FIB on the hydrothermal LMO deposits. The specific surface area of the LMO powder obtained by hydrothermal synthesis was 160 m ² / g (determined elsewhere).
In the hypothesis where one would like to impregnate all the available porosity of an El-Cell electrode disc with a diameter of 18 mm and a grammage in LMO of 0.6 mg / cm ² , an equal volume of electrolyte would be necessary. at 2.3 pL. The theoretical density of LMO, d _L Mo, is equal to 4.29 g / cm ³ . The porosity corresponds to the void volume over the total volume occupied by the deposit, which gives the following ratio:
V _empty V 0,2016 porosity = ---- = --------- = 46.4%
Vtotai -3 --- + V * m _L_ ₊ v - ^ + 0.12016 ^a LM0 d _LM0 4.29
The porosity obtained by this calculation (46.4%) is very close to the porosity estimated by measuring the mass of the deposit and its average thickness (40-50%).
It can therefore be concluded that the porosity in the layers of LMO deposited by the process according to the invention is mainly open porosity.
Example 6: Manufacture of a battery using electrodes according to the invention
Several anodes, respectively cathodes, in thin layers were produced according to Example 3, respectively Example 2. These electrodes were covered with a porous layer from a suspension of nanoparticles of Li ₃ PO ₄ as indicated below. .
at. Production of a suspension of Li ₃ PO ₄ nanoparticles
Two solutions have been prepared:
11.44 g of CH ₃ COOLi, 2H ₂ O were dissolved in 112 ml of water, then 56 ml of water were added with vigorous stirring to the medium in order to obtain a solution A.
4.0584 g of H ₃ PO ₄ were diluted in 105.6 ml of water, then 45.6 ml of ethanol were added to this solution in order to obtain a second solution called hereinafter solution B.
Solution B was then added, with vigorous stirring, to solution A.
The solution obtained, perfectly clear after disappearance of the bubbles formed during mixing, was added to 1.2 liters of acetone under the action of a Ultraturrax ™ type homogenizer in order to homogenize the medium. White precipitation suspended in the liquid phase was immediately observed.
The reaction medium was homogenized for 5 minutes and then was kept for 10 minutes with magnetic stirring. Decanted for 1 to 2 hours. The supernatant was discarded and the remaining suspension was centrifuged for 10 minutes at 6000 rpm. Then 300 ml of water were added to resuspend the precipitate (use of a sonotrode, magnetic stirring). With vigorous stirring, 125 ml of a sodium tripolyphosphate solution at 100 g / l were added to the colloidal suspension thus obtained. The suspension thus became more stable. The suspension was then sonicated using a sonotrode. The suspension was then centrifuged for 15 minutes at 8000 rpm. The pellet was then redispersed in 150 ml of water. Then the suspension obtained was again centrifuged for 15 minutes at 8000 rpm and the pellets obtained redispersed in 300 ml of ethanol in order to obtain a suspension suitable for carrying out an electrophoretic deposition.
Agglomerates of approximately 100 nm consisting of primary particles of Li ₃ PO ₄ of 10 nm were thus obtained in suspension in ethanol.
b. Realization on the anode and cathode layers previously developed of a porous layer from the suspension of nanoparticles of Li ₃ PO ₄ previously described in part a)
Thin porous layers of Li ₃ PO ₄ were then deposited by electrophoresis on the surface of the anodes and cathodes previously produced by applying an electric field of 20V / cm to the suspension of nanoparticles of Li ₃ PO ₄ previously obtained, for 90 seconds to obtain a layer of 1.5 μm. The layer was then air dried at 120 ° C and then a calcination treatment at 350 ° C for 60 minutes was carried out on this previously dried layer in order to remove all traces of organic residues.
vs. Creation of an electrochemical cell
After depositing 1.5 μm of porous Li ₃ PO ₄ on the LiCoO ₂ electrode prepared according to Example 2 and on the Li ₄ Ti ₅ 0i ₂ electrode prepared according to Example 3, the two subsystems were stacked with so that the films of Li ₃ PO ₄ are in contact. This stack was then hot pressed under vacuum.
To do this, the stack was placed under a pressure of 1.5 MPa and then dried under vacuum for 30 minutes at 10 ' ³ bar. The press plates were then heated to 450 ° C with a speed of 4 ° C / seconds. At 450 ° C, the stack was then thermocompressed under a pressure of 45 MPa for 1 minute, then the system was cooled to room temperature.
Once the assembly was completed, a rigid, multilayer system consisting of an assembled cell was obtained.
This assembly was then impregnated in an electrolytic solution comprising PYR14TFSI and LiTFSI at 0.7 M. The ionic liquid instantly returns by capillarity to the porosities. The system was kept immersed for 1 minute, then the surface of the cell stack was dried with an N ₂ blade.
d. Realization of a battery comprising several electrochemical cells
Several anodes, respectively cathodes, in thin layers, were produced according to Example 3, respectively Example 2. These electrodes were covered with a porous layer from a suspension of nanoparticles of Li ₃ PO ₄ as indicated below.
After having deposited 1.5 μm of porous Li ₃ PO ₄ on each of the electrodes (LiCoO ₂ and Li ₄ Ti ₅ 0i ₂ ) previously produced, the two subsystems were stacked so that the films of Li ₃ PO ₄ are in contact. This stack comprising an alternating succession of cathode and anode in thin layers covered with a porous layer and whose films of Li ₃ PO ₄ were in contact, was then hot pressed under vacuum.
To do this, the stack was placed under a pressure of 1.5 MPa and then dried under vacuum for 30 minutes at 10 ' ³ bar. The press plates were then heated to 450 ° C with a speed of 4 ° C / seconds. At 450 ° C, the stack was then thermocompressed under a pressure of 45 MPa for 1 minute, then the system was cooled to room temperature.
Once the assembly was carried out, a rigid, multilayer system consisting of several assembled cells was obtained.
This assembly was then impregnated in an electrolytic solution comprising PYR14TFSI and LiTFSI at 0.7 M. The ionic liquid instantly returns by capillarity to the porosities. The system was kept immersed for 1 minute, then the surface of the cell stack was dried with an N ₂ blade.
A lithium ion battery comprising several electrochemical cells, each comprising electrodes according to the invention, was thus obtained.

权利要求:
Claims (3)
[1" id="c-fr-0001]
1. A method of manufacturing a porous electrode in a thin layer, said electrode comprising a layer deposited on a substrate, said layer being free of binder and having a porosity greater than 30% by volume, and preferably less than 50% by volume , and pores with an average diameter of less than 50 nm, said method being characterized in that:
(A) a colloidal suspension is supplied comprising aggregates of nanoparticles of at least one material P with an average primary diameter D ₅₀ less than or equal to 80 nm, and preferably less than or equal to 50 nm, said aggregates having an average diameter included between 80 nm and 300 nm (preferably between 100 nm and 200 nm), (b) a substrate is supplied, (c) a layer of porous electrode, preferably mesoporous, is deposited on said substrate by electrophoresis or by dip-coating , from said colloidal suspension supplied in step (a), (d) drying said layer obtained in step (c), preferably under an air flow, (e) optionally, consolidation of the layer porous, preferably mesoporous electrode obtained in step (d) by pressing and / or heating.
2. Method of manufacturing a porous electrode according to claim 1, in which:
(a1) a colloidal suspension comprising nanoparticles of at least one material P with an average primary diameter D _{50 of} less than or equal to 80 nm, and preferably less than or equal to 50 nm, is supplied;
(a2) the nanoparticles present in said colloidal suspension are destabilized so as to form aggregates of particles with an average diameter of between 80 nm and 300 nm, preferably between 100 nm and 200 nm, said destabilization preferably taking place by adding 'a destabilizing agent such as a salt, preferably LiOH;
(b) supplying a substrate;
(c) a layer of mesoporous electrode is deposited on said substrate by electrophoresis or by dip-coating, starting from said colloidal suspension comprising the aggregates of nanoparticles obtained in step (a2) (d) drying said layer, preferably under an air flow;
(e) optionally, consolidation of the mesoporous electrode layer obtained in step (d) by pressing and / or heating.
3. Method according to claim 1 or 2, wherein the electrophoretic deposit obtained in step (c) has a thickness less than 10 pm, preferably less than 8 pm, and even more preferably between 1 pm and 6 pm.
4. Method according to one of claims 1 to 3, wherein the diameter of said nanoparticles is between 10 nm and 50 nm, preferably between 10 nm and 30 nm.
5. Method according to any one of claims 1 to 4, in which the average pore diameter is between 2 nm and 80 nm, preferably between 2 nm and 50 nm, preferably between 6 nm and 30 nm and again more preferably between 8 nm and 20 nm.
6. Method according to any one of the preceding claims, in which the porous thin layer electrode has a porosity of between 35% and 50% by volume, and even more preferably between 40% and 50% by volume.
7. Method according to any one of claims 1 to 6, in which said electrode is a cathode, and said material P is selected from the group formed by:
o the oxides LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiMn ^ sNio.sCU, LiMn ₁₅ Ni ₀ 5. _x X _x O ₄ where X is selected from Al, Fe, Cr, Co, Rh, Nd, other earths rare such as Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and where 0 <x <0.1, LiMn ₂ . _x M _x O ₄ with M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg or a mixture of these compounds and where 0 <x <0.4, LiFeO ₂ , LiMn _{1 /} 3Ni ₁ / 3Co ₁ / 3O ₂ ,, LiNio.8Coo.i5Alo.o50 _{2 f} o the phosphates LiFePO ₄ , LiMnPO ₄ , LiCoPO ₄ , LiNiPO ₄ , Li ₃ V ₂ (PO ₄ ) ₃ ; the phosphates of formula LiMM'PO ₄ , with M and M '(M # M') selected from Fe, Mn, Ni, Co, V;
o all the lithiated forms of the following chalcogenides: V ₂ O ₅ , V ₃ O ₈ , TiS ₂ , titanium oxysulfides (TiO _y S _z with z = 2-y and 0.3 <y <1), oxysulfides of tungsten (WO _y S _z with 0.6 <y <3 and 0.1 <z <2), CuS, CuS ₂ , preferably Li _x V ₂ O ₅ with 0 <x <2, Li _x V ₃ O ₈ with 0 <x <1.7, l_i _x TiS ₂ with 0 <x <1, titanium and lithium oxysulfides Li _x TiO _y S _z with z = 2-y, 0.3 <y <1, Li _x WO _y S _z , Li _x CuS, Li _x CuS ₂ .
8. Method according to any one of claims 1 to 7, in which said electrode is an anode, and said material P is selected from the group formed by:
o lithiated iron phosphate (of typical formula LiFePO ₄ );
o mixed oxynitrides of silicon and tin (of typical formula Si _a Sn _b O _y N _z with a> 0, b> 0, a + b <2, 0 <y <4, 0 <z <3) (also called SiTON), and in particular SiSno, ₈ 70i, ₂ N ₁₇₂ ; as well as the oxynitride-carbides of typical formula Si _a Sn _b C _c O _y N _z with a> 0, b> 0, a + b <2, 0 <c <10, 0 <y <24, 0 <z <17;
o nitrides of type Si _x N _y (in particular with x = 3 and y = 4), Sn _x N _y (in particular with x = 3 and y = 4), Zn _x N _y (in particular with x = 3 and y = 2), Li ₃ . _x M _x N (with 0 <x <0.5 for M = Co, 0 <x <0.6 for M = Ni, 0 <x <0.3 for M = Cu); If ₃ . _x M _x N ₄ with M = Co or Fe and 0 <x <3.
o the oxides SnO ₂ , SnO, Li ₂ SnO ₃ , SnSiO ₃ , Li _x SiO _y (x> = 0 et2>y> 0), Li ₄ Ti ₅ 0i ₂ , SnB ₀ , 6Po, 40 ₂ , g and TiO ₂ .
9. Method according to any one of the preceding claims, in which after step (d) or step (e) is deposited, preferably by the technique of depositing atomic layers ALD, during a step (f ) a layer of an electrically insulating material on and inside the pores of the porous layer.
10. The method of claim 9, wherein the electrically insulating material is chosen from AI ₂ O ₃ , SiO ₂ , ZrO ₂ .
11. Method according to any one of claims 1 to 8, in which after step (d) or step (e) is deposited, preferably by ALD, during a step (f) a layer of an ionic conductive material chosen from Li ₃ PO ₄ , Li ₃ BO ₃ , lithium lanthanum zirconium oxide, preferably Li ₇ La ₃ Zr ₂ 0i ₂ , on and inside the pores of the porous layer.
12. Use of a method according to any one of claims 1 to 11 for the manufacture of porous thin layer electrodes, in electronic, electrical or electrotechnical devices, and preferably in devices selected from the group formed by: batteries, capacitors, supercapacitors, capacitors, resistors, inductors, transistors, photovoltaic cells.
13. Method for manufacturing a thin-film battery, implementing the method for manufacturing a porous thin-layer electrode according to one of claims 1 to 11.
14. A method of manufacturing a thin film battery according to claim 13 and comprising the steps of:
(1) Supply of a colloidal suspension comprising nanoparticles of at least one cathode material of average primary diameter D ₅₀ less than or equal to 50 nm;
[2" id="c-fr-0002]
(2) Supply of a colloidal suspension comprising nanoparticles of at least one anode material with an average primary diameter D ₅₀ less than or equal to 50 nm;
[3" id="c-fr-0003]
(3) Supply of at least two flat, preferably metallic, conductive substrates, said conductive substrates being able to serve as battery current collectors, (4) Deposit of at least one thin layer of cathode, respectively of anode, by dip-coating or by electrophoresis, preferably by galvanostatic electrodeposition by pulsed currents, from said suspension of nanoparticles of material obtained in step (1), respectively in step (2), on said substrate obtained in step (3), (5) Drying of the layer thus obtained in step (4), (6) Optionally, deposition by ALD of a layer of an electrically insulating material on and inside the pores of the cathode and / or anode layer obtained in step (5), (7) Electrophoresis deposition of a film of an electrically insulating material or of an ionic conductive material from a colloidal suspension of nanoparticles of this material aggregated from mean primary diameter D ₅₀ less than or equal to 50 nm and mean diameter D ₅₀ of approximately 100 nm on the cathode layer, respectively anode layer obtained in step (5) and / or step (6), (8) Drying of the layer thus obtained in step (7), (9) The stack comprising an alternating succession of cathode and anode layers in thin layers offset laterally, (10) Hot pressing of the layers anode and cathode obtained in step (9) so as to juxtapose the films obtained in step (8) present on the anode and cathode layers, (11) Impregnation of the structure obtained in step (10) by a phase carrying lithium ions leading to the production of an impregnated structure.
15. Method according to any one of claims 13 to 14, in which after step -11-:
successively, alternately, on the impregnated structure:
at least a first layer of parylene and / or polyimide on said battery, at least a second layer composed of an electrically insulating material by ALD (Atomic Layer Deposition) on said first layer of parylene and / or polyimide, and on the alternating succession of at least a first and at least a second layer is deposited a layer for protecting the battery against mechanical damage to the battery, preferably silicone, epoxy resin, parylene or polyimide thus forming , a battery encapsulation system, the battery thus encapsulated is cut along two cutting planes in order to expose anode and cathode connections of the battery on each of the section planes, so that the encapsulation system is four of the six faces of said battery, preferably continuously, so as to obtain an elementary battery, successively deposited on and at turn, of these anodic and cathodic connections:
an optional first electronically conductive layer, preferably deposited by ALD, a second layer based on silver-charged epoxy resin, deposited on the first electronically conductive layer, and a third layer based on nickel, deposited on the second layer , and a fourth layer based on tin or copper, deposited on the third layer.
16. The method of claim 15, wherein the anode and cathode connections are located on opposite sides of the stack.
17. Porous electrode with porosity greater than 30% by volume comprising pores with an average diameter less than 80 nm, preferably less than 50 nm, a primary diameter of particles less than 30 nm, characterized in that it comprises a smaller thickness at 10 pm and is free of binder.
18. Porous electrode according to claim 17, characterized in that said pores are impregnated with an electrolyte, preferably a phase carrying lithium ions such as an ionic liquid containing lithium salts, possibly diluted in an organic solvent or a mixture of organic solvents containing a lithium salt which may be different from that dissolved in the ionic liquid.
19. Battery comprising at least one porous electrode capable of being obtained by the method according to any one of claims 1 to 11.
20. Battery according to claim 19, characterized in that all of its electrodes are porous electrodes capable of being obtained by the method according to any one of claims 1 to 11.

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FR3023418B1|2014-07-01|2016-07-15|I Ten|COMPLETELY SOLID BATTERY COMPRISING AN ELECTROLYTE IN RETICULATED SOLID POLYMERIC MATERIAL|

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FR3023417B1|2014-07-01|2016-07-15|I-Ten|COMPLETELY SOLID BATTERY COMPRISING SOLID ELECTROLYTE AND LAYER OF SOLID POLYMERIC MATERIAL|

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FR3046498B1|2015-12-31|2019-11-29|I-Ten|COMPLETELY SOLID BATTERY COMPRISING A SOLID ELECTROLYTE AND A LAYER OF IONIC CONDUCTIVE MATERIAL|CN109888157B|2019-03-19|2021-07-09|合肥国轩高科动力能源有限公司|Diaphragm, preparation method thereof and lithium ion battery comprising diaphragm|

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FR3109671A1|2020-04-28|2021-10-29|Hfg|MANUFACTURING PROCESS OF A POROUS ELECTRODE AND SEPARATOR ASSEMBLY, A POROUS ELECTRODE AND SEPARATOR ASSEMBLY, AND ELECTROCHEMICAL DEVICE CONTAINING SUCH ASSEMBLY|

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FR3109672A1|2020-04-28|2021-10-29|I-Ten|PROCESS FOR MANUFACTURING A POROUS ELECTRODE, AND MICROBATTERY CONTAINING SUCH AN ELECTRODE|

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FR3109670A1|2020-04-28|2021-10-29|I-Ten|PROCESS FOR MANUFACTURING A POROUS ELECTRODE AND SEPARATOR ASSEMBLY, A POROUS ELECTRODE AND SEPARATOR ASSEMBLY, AND MICROBATTERY CONTAINING SUCH ASSEMBLY|

法律状态:
2019-05-24| PLFP| Fee payment|Year of fee payment: 2 |

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2019-11-08| PLSC| Search report ready|Effective date: 20191108 |

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2020-05-15| PLFP| Fee payment|Year of fee payment: 3 |

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2021-05-18| PLFP| Fee payment|Year of fee payment: 4 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1853920A|FR3080957B1|2018-05-07|2018-05-07|MESOPOROUS ELECTRODES FOR THIN FILM ELECTROCHEMICAL DEVICES|

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FR1853920|2018-05-07|FR1853920A| FR3080957B1|2018-05-07|2018-05-07|MESOPOROUS ELECTRODES FOR THIN FILM ELECTROCHEMICAL DEVICES|

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PCT/FR2019/051028| WO2019215407A1|2018-05-07|2019-05-06|Porous electrodes for electrochemical devices|

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CA3098636A| CA3098636A1|2018-05-07|2019-05-06|Porous electrodes for electrochemical devices|

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US17/049,977| US20210074991A1|2018-05-07|2019-05-06|Porous electrodes for electrochemical devices|

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EP19728499.5A| EP3766115A1|2018-05-07|2019-05-06|Porous electrodes for electrochemical devices|

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CN201980029285.2A| CN112088450A|2018-05-07|2019-05-06|Porous electrode for electrochemical device|

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JP2020561039A| JP2021523514A|2018-05-07|2019-05-06|Porous electrodes for electrochemical devices|

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SG11202010865RA| SG11202010865RA|2018-05-07|2019-05-06|Porous electrodes for electrochemical devices|