Method for producing a dense layer usable as an electrode and / or electrolyte for a lithium-ion battery and a lithium-ion microbattery obtained therefrom

Abstract

Method for producing a dense layer, comprising the following steps: providing a substrate and providing a suspension of non-aggregated nanoparticles of material P; depositing a layer on the substrate using the suspension; drying the layer obtained thereby; densifying the dried layer by mechanical compression and / or heat treatment; the method being characterized in that the suspension of non-aggregated nanoparticles of material P comprises nanoparticles of material P having a particle size distribution characterized by its D50 value, such that: - the particle size distribution comprises nanoparticles of material P having a first particle size D1 between 20 nm and 50 nm, and nanoparticles of material P having a second particle size D2, characterized in that the D50 of the second particle size D2 is at least five times smaller than that of D1; or - the distribution comprises nanoparticles of material P having an average size of less than 50 nm and a ratio of the standard deviation to the average size of greater than 0.6.

Description

Technical Field

[0001] The present invention relates to the production of dense layers suitable for use in electrochemical devices, particularly as electrode or electrolyte layers. These layers are particularly useful in multilayer batteries, such as lithium-ion microbatteries. They are prepared from inorganic nanoparticles that may optionally be functionalized with an organic coating, which may be a polymer coating.

[0002] The invention also relates to a new method for producing these dense layers from nanoparticles. It also relates to layers obtained using this method, and to multilayer microbatteries comprising at least one layer obtained using this method.

[0003] The invention also relates to a novel method for producing a lithium-ion battery, wherein at least one dense electrode layer is deposited using the novel method for producing a dense layer, and wherein a porous layer is also deposited. Background Art

[0004] Among the various proposed electrochemical energy storage technologies, lithium-ion batteries offer the best energy density. The electrodes used to produce lithium-ion batteries have varying structures and chemical compositions. Numerous articles and patents describe the manufacturing methods of lithium-ion batteries, and a good overview is provided in the publication "Advances in Lithium-Ion Batteries" (by W. van Schalkwijk and B. Scrosati, Kluever Academic / Plenum Publishers, 2002).

[0005] There is a growing demand for microbatteries, i.e. very small rechargeable batteries that can be integrated into electronic cards; these electronic circuits are used in many areas, such as secure transaction cards, electronic tags, implantable medical devices and various micromechanical systems.

[0006] According to the prior art, electrodes for lithium-ion batteries can be manufactured using coating techniques (particularly roll coating, blade coating, tape casting, and slot die coating). Using these methods, the active material used to produce the electrodes is in powder form, with an average particle size between 5 and 15 μm in diameter. These particles are incorporated into an ink formed from these particles and deposited on the surface of a substrate.

[0007] These technologies can produce layers with thicknesses ranging from approximately 50 μm to approximately 400 μm. Depending on the thickness of the layer, its porosity, and the size of the active particles, the power and energy of the battery can be adjusted. For the production of microbatteries, even smaller thicknesses are sought.

[0008] The ink (or paste) deposited to form the electrode contains particles of active material, but also an (organic) binder, carbon powder to provide electrical contact between the particles, and a solvent that evaporates during the electrode drying step. To improve the quality of the electrical contact between the particles and compact the deposited layer, a calendering step is performed on the electrode. After this compression step, the active particles of the electrode occupy approximately 60% of the deposited volume, which means that typically 40% of the porosity remains between the particles.

[0009] The contacts between each particle are essentially point-like, and the electrode structure is porous. The pores are filled with an electrolyte, which can be a liquid (an aprotic solvent in which the lithium salt is dissolved) or a polymer gel that is more or less impregnated with the lithium salt. The thickness of a lithium-ion battery electrode is generally between 50 μm and 400 μm, and lithium ions are transported through the thickness of the electrode through the pores filled with the electrolyte (containing the lithium salt). The diffusion rate of lithium through the thickness of the electrode varies depending on the number and size of the pores.

[0010] For batteries to function properly, lithium ions must diffuse through the thickness of the particles and the electrode. Diffusion of active materials within particles is slower than diffusion through the electrolyte, a liquid or gel-like substance that impregnates porous electrodes. Slow diffusion within electrode particles contributes to the battery's series resistance. Furthermore, achieving satisfactory battery power requires a reduction in particle size; in standard lithium-ion batteries, particle sizes typically range from 5μm to 15μm.

[0011] Furthermore, the power and energy of the battery can be adjusted by adjusting the thickness of the layer and the size and density of the active particles contained in the ink. Increasing the energy density inevitably compromises the power density. High-power batteries must use thin, high-porosity electrodes and separators, while increasing the energy density, on the other hand, requires increasing these thicknesses and reducing the porosity. John Newman's article "Optimization of Porosity and Thickness of a Battery Electrode by Means of a Reaction-Zone Model," published in J. Electrochem. Soc., Vol. 142, No. 1, January 1995, shows the influence of the thickness of the electrode and its porosity on its discharge rate (power) and energy density.

[0012] However, increasing the porosity of an electrode tends to reduce the battery's energy density: to increase the electrode's energy density, the porosity must be reduced. In current lithium-ion batteries, it's essentially the electrolyte-filled pores between the active particles that allow lithium ions to diffuse through the electrode. In the absence of electrolyte-filled pores, lithium ions are transported from one particle to another at the contacts between the particles, which are essentially point contacts. Consequently, resistance to lithium ion transport renders the battery inoperable.

[0013] Furthermore, to function properly, the pores of the electrodes must be filled with electrolyte. This filling is only possible when these pores are open. Furthermore, depending on the size of the pores and their tortuosity, impregnating the electrodes with electrolyte can become very difficult or even impossible. As the porosity of the impregnating electrolyte decreases, the electrical resistance of the layer decreases, and its ionic resistance increases. When the porosity drops below 30% or even 20%, the ionic resistance increases significantly, as some pores are subsequently able to close again, preventing the electrolyte from wetting the electrodes.

[0014] Therefore, once attempts are made to create non-porous electrode films to increase energy density, the thickness of these films must be limited to less than 50 μm, preferably less than 25 μm, to allow rapid diffusion of lithium ions in the solid without loss of power.

[0015] To produce dense films, the main process used involves vacuum deposition of thin films of lithium-intercalating electrode materials. This technique produces dense films without pores or binders, resulting in excellent energy density and satisfactory temperature characteristics.

[0016] The absence of pores enables the diffusional transport of lithium ions through the membrane without the use of organic electrolytes based on polymers or lithium salt-containing solvents.

[0017] This completely inorganic film offers excellent performance in terms of aging, safety and temperature characteristics.

[0018] PVD (Physical Vapor Deposition) is currently the most commonly used technology for manufacturing thin-film microbatteries. In fact, these products require thin films without pores and other point defects to ensure low resistivity and proper ion conduction required for the normal operation of electrochemical devices.

[0019] Deposition rates achieved using this technique are on the order of 0.1 to 1 μm per hour. PVD deposition produces very high-quality thin films that are virtually free of point defects and can be deposited at relatively low temperatures. However, differences in evaporation rates between different elements make it difficult to deposit complex compounds and control the stoichiometry of the layer using this technique. While this technique is well-suited for producing thin layers with simple chemical compositions, increasing the deposition thickness results in deposition times that are too long for industrial application in the low-cost product segment.

[0020] Furthermore, the vacuum deposition techniques used to produce such thin films are very costly and difficult to implement industrially over large surface areas with high throughput.

[0021] Other technologies currently available for producing dense ceramic membranes include densification based on the deposition of dense particles or, in fact, the use of sol-gel type techniques to obtain the membrane. Sol-gel technology involves depositing a polymer lattice obtained after hydrolysis, polymerization and condensation steps on the surface of a substrate. The sol-gel transition occurs during the evaporation of the solvent, which accelerates the surface reaction process. This technology can produce very thin dense deposits. The membranes thus obtained have thicknesses of the order of about 100 nanometers. These thicknesses are too small to achieve reasonable energy storage in battery applications.

[0022] In order to increase the thickness of the deposit without risking cracks or fissures, it is necessary to carry out several successive steps. However, this reduces the industrial productivity of the technique as soon as the thickness of the layer is increased.

[0023] Ceramic electrodes and / or electrolyte membranes for batteries can also be produced by powder sintering. For this purpose, a slurry containing ceramic particles and an organic binder is deposited in thin film form to obtain a precursor strip commonly known as a "green sheet".

[0024] The precursor strips are then calcined to remove organic matter and sintered at high temperatures to produce sheets of ceramic material.

[0025] In this case, the thin metal film used to collect the current on these electrodes is also deposited using the inking technique. The metal powder is also sintered simultaneously with the "green sheet." During the sintering step, the pores between the particles of the ceramic material are filled, which causes the strip to shrink.

[0026] Sintering the current collector with the ceramic membrane can accommodate the dimensional changes of the ceramic membrane and the metal current collector and prevent the occurrence of cracks.

[0027] These methods operate at very high temperatures. However, battery materials are often temperature sensitive and degrade rapidly when subjected to such heat treatments.

[0028] To lower this sintering temperature, the use of nanoparticles has been proposed. This involves creating dense deposits of non-aggregated nanoparticles. These deposits can be easily sintered at relatively low temperatures. This low temperature makes it possible to sinter directly onto metal substrates.

[0029] However, it has been observed that these deposits, when they are produced on a metal substrate, will, depending on the thickness of the deposit, its compactness, its particle size, lead to the appearance of cracks during the drying and / or sintering steps.

[0030] Electrophoretic nanoparticle deposition techniques have been used to increase the density of the deposit, thereby promoting low-temperature sintering with fewer cracks; this is described in several patent applications, such as WO 2013 / 064 773, WO 2013 / 064 776, WO 2013 / 064 777, and WO 2013 / 064 779 (Fabien Gaben). Thermal agglomeration is carried out at particularly low temperatures because the nanoparticles are small in size, preferably less than 100 nm.

[0031] The present invention seeks to at least partially alleviate the above-mentioned drawbacks of the prior art.

[0032] More specifically, the problem addressed by the present invention is to provide a method for manufacturing a dense ceramic layer directly on a metal substrate, which method is simple, safe, fast, easy to implement, and low-cost.

[0033] The present invention also aims to produce dense solid (ceramic) layers suitable for lithium-ion microbatteries, with few or no defects and pores.

[0034] The present invention also aims to provide a dense electrode and a dense electrolyte with high ionic conductivity, stable mechanical structure, good thermal stability and long service life.

[0035] Another object of the present invention is to provide a method for manufacturing an electronic, electrical or electrotechnical device (such as a microbattery, a capacitor, a supercapacitor, a photovoltaic cell) comprising the dense electrode or the dense electrolyte of the present invention. Summary of the Invention

[0036] According to the invention, this problem is solved by a method for producing a dense layer, comprising the following steps:

[0037] - providing a substrate and providing a suspension of non-aggregated nanoparticles of material P,

[0038] - depositing a layer on said substrate using a suspension of primary nanoparticles of material P;

[0039] - drying the resulting layer,

[0040] - densification of the dried layer by mechanical compression and / or heat treatment,

[0041] It will be appreciated that the drying step and the densification step may be performed at least partially simultaneously, or at elevated temperatures.

[0042] The method constituting the first object of the present invention is characterized in that the suspension of non-aggregated nanoparticles of material P comprises nanoparticles of material P having a specific particle size distribution, which allows to obtain a density greater than 75% after deposition. 50 Value representation.

[0043] This particle size distribution can be obtained by any of the following methods:

[0044] - continuous: in this case, the ratio of standard deviation / mean particle size of the nanoparticles of material P must be greater than 0.6 and the mean size of the primary nanoparticles of material P must be less than or equal to 50 nm; or

[0045] - Discontinuous: In this case, the particle size distribution of the nanoparticles of material P comprises nanoparticles of a first particle size D1 between 50 nm and 20 nm and nanoparticles of a second particle size D2 at least five times smaller than D1. Advantageously, the particles of size D1 represent 50% to 75% of the total mass of the nanoparticles.

[0046] The suspension of non-aggregated nanoparticles of the material P may be obtained using a monodisperse suspension having a particle size of D1, and / or the suspension of nanoparticles having a particle size of D2 may be obtained using a monodisperse suspension.

[0047] According to the invention, the deposition of the hard, dense ceramic layer is carried out by electrophoresis, dip coating, inkjet printing, roller coating, slot coating, curtain coating or doctor blade coating.

[0048] After deposition, the density of the dried layer is greater than 75% due to the size distribution of its constituent nanoparticles.This density can be further increased by densifying the dried layer by mechanical compression and / or by thermal treatment.

[0049] A second object of the present invention is a dense layer obtainable by the method described in the first object. It can be chosen in particular from anodes, cathodes and / or electrolytes for lithium-ion batteries.

[0050] A third object of the present invention is a dense layer in an electrochemical, electronic, electrical or electrotechnical device, such as a battery (preferably a lithium-ion battery), a capacitor, a supercapacitor, a capacitor, a resistor, an induction coil, or a transistor, which can be obtained by the method of the present invention. The dense layer can in particular be an anode layer, a cathode layer and / or an electrolyte layer.

[0051] A fourth object of the present invention is a method for manufacturing a dense layer for a lithium-ion battery, which method has the features of the above-mentioned method for manufacturing a dense layer, wherein all embodiments can be implemented for manufacturing a dense layer for a lithium-ion battery.

[0052] A final object of the present invention is an electrochemical device, in particular a microbattery, in particular a lithium-ion microbattery, comprising at least one dense layer according to the second object of the present invention.

[0053] In one embodiment, the lithium-ion microbattery comprises an anode and a cathode, which are dense layers according to the present invention. The thickness of the anode and / or cathode may be about 1 μm to about 50 μm.

[0054] In a first variant, the electrolyte layer can also be a dense layer as described herein. In a second variant, the microbattery comprises a liquid electrolyte impregnated in a porous separator that separates the anode and cathode. The thickness of the electrolyte layer or separator is advantageously between about 1 μm and about 20 μm, preferably between about 3 μm and about 10 μm.

[0055] In another embodiment, only the electrolyte layer is the dense layer described in the present invention. DETAILED DESCRIPTION

[0056] 1. definition

[0057] In the context of this document, the size of a particle is defined by its largest dimension. The term "nanoparticle" refers to any particle or object of nanometer size having at least one dimension less than or equal to 100 nm. This dimension D is herein referred to as dimension D. 50 express.

[0058] The term "nanoparticles" is used herein to refer to primary particles, as opposed to particles formed by aggregation or agglomeration of several primary particles. Such agglomerates can be reduced to nanoparticles (in the sense understood herein) by a dispersion operation, for example by grinding or ultrasound treatment.

[0059] The density of the layer is expressed here as a relative value (for example as a percentage) by dividing the actual density of the layer (here d 层 denoted) and the theoretical density of the constituent solid materials (denoted here by d 理论 Therefore, the porosity of the layer (expressed as a percentage) is determined as follows:

[0060] Porosity [%] = [(d 理论 –d 层 ) / d 理论 ]x100.

[0061] In the context of this document, an electrically insulating material or layer, preferably an ionically conductive layer, is one in which the resistivity (resistance to electron flow) is greater than 10 5 Ω·cm material or layer. The term "ionic liquid" refers to any liquid salt capable of conducting electricity, distinguished from all molten salts by having a melting point below 100°C. Some of these salts remain liquid at ambient temperature and do not solidify even at very low temperatures. Such salts are called "room temperature ionic liquids."

[0062] The term "mesoporous" material refers to any solid having so-called "mesopores" within its structure, which have a size intermediate between micropores (less than 2 nm in width) and macropores (greater than 50 nm in width), i.e., a size between 2 nm and 50 nm. This terminology is consistent with the terminology adopted by IUPAC (International Union of Pure and Applied Chemistry), which serves as a reference for those skilled in the art. Therefore, the term "nanopore" is not used herein, even though the mesopores as defined above have nanometer dimensions according to the definition of nanoparticles, it should be understood that pores smaller in size than mesopores are referred to as "micropores" by those skilled in the art.

[0063] An overview of the concept of porosity (and the above-mentioned terminology) is given in the article "Texture des matériaux pulvérulents ou poreux" by F. Rouquerol et al., published in the collection "Techniques de l'Ingénieur", section P1050 of the analysis and characterization papers; this article also introduces porosity characterization techniques, in particular the BET method.

[0064] According to the present invention, the term "mesoporous layer" refers to a layer having mesopores. As will be explained below, in these layers, the mesopores contribute significantly to the total porous volume; this fact is conveyed by the expression "mesoporous layer having a porosity greater than X volume %" used in the following description, where X % is preferably greater than 25% of the total volume of the layer, more preferably greater than 30%, and even more preferably between 30 and 50%.

[0065] According to the IUPAC definition, the term "aggregate" refers to a weakly bonded combination of primary particles. In this case, these primary particles are nanoparticles whose diameters can be measured by transmission electron microscopy. According to techniques known to those skilled in the art, the aggregates of the primary nanoparticles of aggregation can usually be destroyed (i.e., reduced to primary nanoparticles) and suspended in a liquid phase under the action of ultrasound.

[0066] According to the IUPAC definition, the term "agglomerate" refers to a strongly bonded grouping of primary particles or aggregates.

[0067] According to the present invention, the term "electrolyte layer" refers to a layer within an electrochemical device that enables the device to operate according to its end use. The electrolyte layer is an ion conductor, but it is electrically insulating. For example, in the case of a secondary lithium-ion battery, the term "electrolyte layer" refers to a dense electrolyte layer in which lithium cations migrate, or a "porous inorganic layer" impregnated with a phase carrying lithium ions. According to the terminology used by those skilled in the art, the porous inorganic layer in an electrochemical device is also referred to herein as a "separator."

[0068] 2. Detailed description

[0069] According to the invention, this problem is solved by using a method for depositing a layer of a suspension of nanoparticles, wherein the sizes of the nanoparticles have a specific type of particle size distribution.

[0070] According to one essential aspect of the present invention, a nanoparticle suspension having a specific nanoparticle size distribution is used, thereby significantly increasing the deposition density of the nanoparticles before sintering.

[0071] Obtaining the densest deposit possible before sintering will have the potential to reduce shrinkage and lower the risk of cracking. To achieve the densest possible deposit, not only does the particle size distribution of the nanoparticles need to be perfectly controlled, but the deposition of these nanoparticles also needs to be as dense as possible without agglomeration.

[0072] To obtain this dense deposit, electrophoretic deposition techniques can be used from dilute suspensions, or indeed from concentrated, non-aggregated suspensions of these polydisperse nanoparticles, deposited by inking, dip coating, curtain coating, doctor blade coating, slot coating, etc. Obtaining such concentrated suspensions requires the use of stabilizers, which are organic ligands (for example of the PVP type) to prevent aggregation phenomena between the nanoparticles. These ligands will be removed at the beginning of the sintering heat treatment: usually, an intermediate temperature ramp is carried out in order to remove all these organic compounds before sintering.

[0073] The viscosity of the suspension used for deposition depends essentially on the nature of the liquid phase (solvent), the size of the particles, and their concentration (expressed as a dry extract). The viscosity of the suspension, along with the parameters of the deposition method (particularly the speed of movement or throughput in the liquid), determines the thickness of the deposit. Depending on these parameters, which are inherent to the deposition technique, the viscosities typically used for dip coating, curtain coating, or slot coating vary widely, ranging from approximately 20 cP to approximately 2000 cP, measured at 20°C. Colloidal suspensions used for deposition are often referred to as "inks," regardless of their viscosity.

[0074] Once these organic compounds are removed, the nanoparticles come into contact and the consolidation process begins. The surfaces of the nanoparticles join together at the points of contact; this phenomenon is called "necking." During sintering, these contact points, now forming bonding zones, increase through diffusion until they fill the voids left by the initial porosity of the deposit. The filling of these voids is responsible for shrinkage.

[0075] Furthermore, in order to produce thick, crack-free deposits on metal substrates with a final porosity of less than 15%, preferably less than 10%, it is necessary to maximize the compactness of the initial nanoparticle deposition while maintaining the nano-effect. This makes it possible to reduce the consolidation temperature and keep it compatible with the use of metal substrates.

[0076] According to the present invention, colloidal nanoparticle suspensions are used in which the average nanoparticle size is no more than 100 nm. In addition, these nanoparticles have a relatively wide particle size distribution. When this particle size distribution is observed to be approximately Gaussian, the ratio of the standard deviation to the mean radius of the nanoparticles (σ / R 平均值 ) must be greater than 0.6.

[0077] In order to increase the density of the initial deposit before sintering, a mixture of two sized nanoparticle populations can also be used. In this case, the average diameter of the largest distribution should not exceed 100 nm, preferably not more than 50 nm. The first largest nanoparticle population may have a narrower particle size distribution, with a σ / R 平均值 The ratio of the two groups of nanoparticles is less than 0.6. This "large" nanoparticle population should account for 50% to 75% of the sediment dry extract (expressed as a mass percentage relative to the total mass of nanoparticles in the sediment). Therefore, the second nanoparticle population accounts for 50% to 25% of the sediment dry extract (expressed as a mass percentage relative to the total mass of nanoparticles in the sediment). The average diameter of the particles in this second nanoparticle population should be at least 5 times smaller than the average diameter of the largest nanoparticle population. Like the largest nanoparticles, the particle size distribution of this second nanoparticle population may be narrower, with a σ / R 平均值 The ratio may be less than 0.6. Preferably, the average diameter of the second nanoparticle population is at least one-fifteenth, preferably at least one-twelfth, of the largest nanoparticle population; this facilitates densification of the layer after its deposition.

[0078] In any case, both populations of nanoparticles should show agglomeration in the ink produced. Furthermore, these nanoparticles may advantageously be synthesized in the presence of a ligand or organic stabilizer to prevent aggregation or agglomeration of the nanoparticles.

[0079] The preparation of colloidal suspensions by wet nanomilling allows for the achievement of relatively broad particle size distributions. However, depending on the nature of the milled material, its "brittleness", and the applied reduction factor, the primary nanoparticles can be damaged or amorphized.

[0080] The materials used in lithium-ion batteries are particularly sensitive; even the slightest change in their crystalline state or chemical composition can lead to a decrease in electrochemical performance. For this type of application, nanoparticles of the desired primary nanoparticle size are preferably prepared directly from suspension by precipitation using solvothermal or hydrothermal methods.

[0081] These precipitation-based nanoparticle synthesis methods yield uniformly sized primary nanoparticles with reduced size distribution, good crystallinity, and purity. These methods also enable the production of very small particles, potentially less than 10 nm, in a non-aggregated state. To achieve this, the ligand must be added directly to the synthesis reactor to prevent the formation of agglomerates and aggregates during the synthesis process. For example, PVP can be used to perform this function.

[0082] Since the particle size distribution of the non-agglomerated nanoparticles obtained by precipitation is relatively narrow, it is necessary to preferably adopt a colloidal suspension preparation strategy that mixes the two particle size distributions according to the above rules in order to maximize the compactness of the deposit before sintering. This will allow the production of relatively thick deposits directly on the metal substrate after sintering, with little or no risk of cracking during the sintering heat treatment, which will be carried out at relatively low temperatures due to the small size of the nanoparticles used.

[0083] Then use bimodal nanoparticle suspension to deposit dense layer, then make dense layer densification by low temperature heat treatment, and be particularly suitable for use as electrode or electrolyte of electrochemical device (such as lithium ion battery).Can use various methods to deposit these layers, particularly electrophoresis, be selected from the printing method of inkjet printing and flexographic printing, and be preferably selected from the coating method of blade coating, roller coating, curtain coating, dip coating, slit coating.These methods are simple, safe, easy to implement, can be industrialized, and may obtain uniform final dense layer.Electrophoresis can deposit uniform layer with high deposition rate on large surface area.Coating technology, particularly dip coating, roller coating, curtain coating or blade coating, can simplify the bath management relevant with electrophoresis, because the composition of bath remains unchanged during by coating deposition.Inkjet printing deposition can produce local deposition.

[0084] Dense electrodes and electrolytes in thick layers can be obtained by the above-described methods using bimodal or polydisperse nanoparticle suspensions and produced in a single step.

[0085] The method of the present invention can produce a dense layer with a density of at least 90% of the theoretical density, preferably at least 95% of the theoretical density, even more preferably at least 96% of the theoretical density, and best at least 97% of the theoretical density, it should be understood that the remainder consists of residual pores consisting of closed cells.

[0086] An embodiment of a dense electrode according to the invention will now be described by way of non-limiting example; in this description certain details of the method according to the invention are explained in more depth.

[0087] Properties of the current collector

[0088] Typically, the substrate used as the current collector in batteries using the dense electrodes of the present invention is metallic, such as a metal plate. The substrate selected must be able to withstand the temperatures of any thermal or thermomechanical treatments to be applied to the layers deposited thereon, and this temperature will depend on the chemical nature of the layers. The substrate is preferably selected from strips made of titanium, molybdenum, chromium, tungsten, copper, nickel, or stainless steel, or any alloy containing at least one of the foregoing elements.

[0089] Generally speaking, the metal plate can be coated with a layer of precious metal, in particular selected from gold, platinum, palladium, titanium, molybdenum, tungsten, chromium or an alloy mainly containing at least one or more of these metals, or coated with a layer of ITO type conductive material (which has the advantage of also being able to serve as a diffusion barrier layer).

[0090] In this example, we will use a 316L stainless steel plate with a thickness of 10 microns.

[0091] Deposition of dense electrode layers by dip coating

[0092] Generally speaking, the electrode layer can be deposited on the metal surface of the current collector, or on another dense or porous inorganic layer, such as a dense electrolyte layer or a porous separator.

[0093] Dip coating can be used to deposit bimodal nanoparticles regardless of the chemical nature of the nanoparticles used; obviously, the other deposition techniques mentioned above can also be used.

[0094] For example, to produce dense Li4Ti5O 12 ceramic deposits, we can produce inks composed of nanoparticles of two different sizes, Li4Ti5O 12 In the case of fabrication, about 5 nm Li4Ti5O was synthesized by the alcohol thermal route. 12Nanoparticles (see the article "Impact of the Synthesis Parameters on the microstructure of nano-structured LTO prepared by glycothermal routes and 7 Li NMR structural investigations", M. Odziomek, F. Chaput et al., published in J Sol-Gel Sci Technol 89, 225–233 (2019). In this synthesis, ligands were added to limit the aggregation of nanoparticles. These nanoparticles with a diameter of 5 nm were compared with Li4Ti50 nanoparticles with a particle size of 30 nm obtained by hydrothermal synthesis. 12 Nanoparticle binding.

[0095] These nanoparticles were mixed and dispersed with 70% by mass of 30 nm particles and 30% by mass of 5 nm nanoparticles in an ink with a total dry extract of 15% in ethanol and containing PVP as a stabilizer, using ultrasound. Each dip coating process produces only a single layer of relatively limited thickness; the wet layer must be dried. The dip coating deposition and layer drying steps can be repeated as many times as necessary to achieve the desired final layer thickness.

[0096] Although this sequential dip-coating / drying step is time-consuming, the dip-coating deposition method is simple, safe, easy to implement, industrializable, and can produce a uniform and dense final layer.

[0097] Processing and properties of sedimentary layers

[0098] Generally speaking, layers deposited by dip coating must be dried. Once dried, they are thermally treated in two stages. In the first stage, the deposit is held at 400°C for 10 minutes to calcine any organic compounds contained therein. The treatment temperature is then increased to 550°C and held at this temperature for 1 hour to consolidate the deposit.

[0099] The choice of nanoparticle material will obviously depend on the function of the layer to be deposited in the target electrochemical, electrical, or electronic device. Generally speaking, the nanoparticles used in the present invention are inorganic and non-metallic, with the understanding that they can be coated with an organic functionalized layer ("core-shell" type particles); this will be described below. These particles coated with organic layers are included herein under the term "inorganic particles."

[0100] If the layer according to the invention is used as cathode for a battery, in particular a lithium-ion battery, it can be produced, for example, from a material P which is a cathode material selected from:

[0101] - Oxide LiMn2O4, Li 1+x Mn 2-x O4, where 0 < x < 0.15, LiCoO2, LiNiO2, LiMn 1.5 Ni 0.5 O4, LiMn 1.5 Ni 0.5-x X x O4, where X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earth elements Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, where 0 < x < 0.1, LiMn 2-x M x O4, where M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg or a mixture of these compounds, where 0 < x < 0.4, LiFeO2, LiMn 1 / 3 Ni 1 / 3 Co 1 / 3 O2, LiNi 0.8 Co 0.15 Al 0.05 O2, LiAl x Mn 2-x O4, where 0 ≤ x < 0.15, LiNi 1 / x Co 1 / y Mn 1 / z O2, where x + y + z = 10;

[0102] - Phosphates LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2(PO4)3; phosphates of the formula LiMM’PO4, where M and M’ (M ≠ M’) are selected from Fe, Mn, Ni, Co, V;

[0103] - All lithiated forms of the following chalcogenides: V2O5, V3O8, TiS2, titanium oxysulfide (TiO y S z , where z = 2 - y and 0.3 ≤ y ≤ 1), tungsten oxysulfide (WO y S z , where 0.6 < y < 3 and 0.1 < z < 2), CuS, CuS2, preferably Li x V2O5, where 0 < x ≤ 2, LixV3O8, where 0 < x ≤ 1.7, Li x TiS2, where 0 < x ≤ 1, lithium titanium oxysulfide Li x TiO y S z [[ID=并]] S x WOy S z ,Li x CuS,Li x CuS2。

[0104] If the layer according to the invention is used as an anode of a battery, in particular a lithium-ion battery, it can be produced from a material P, for example, which is an anode material selected from:

[0105] - carbon nanotubes, graphene, graphite;

[0106] - lithiated iron phosphate (typical formula LiFePO4);

[0107] - mixed silicon tin oxynitride (typical formula Si a Sn b O y N z where a > 0, b > 0, a + b ≤ 2, 0 < y ≤ 4, 0 < z ≤ 3) (also known as SiTON), in particular SiSn 0.87 O 1.2 N 1.72 ; and the oxynitride - carbide of the typical formula Si a Sn b C c O y N z where a > 0, b > 0, a + b ≤ 2, 0 < c < 10, 0 < y < 24, 0 < z < 17;​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​2.9 and TiO2,

[0110] a complex oxide TiNb2O7 containing from 0 to 10% by mass of carbon, preferably selected from graphene and carbon nanotubes,

[0111] -General formula Li w Ti 1-x M 1 x Nb 2-y M 2 y O 7-z M 3 z A compound wherein M 1 and M 2 Each is at least one element selected from Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs and Sn, M 1 and M 2 are optionally the same or different from each other, wherein M 3 is at least one halogen, wherein 0≤w≤5, 0≤x<1, 0≤y<2 and 0 <z≤0.3。

[0112] If the layer according to the invention is used as electrolyte for batteries, in particular lithium-ion batteries, it can be produced, for example, from a material P which is an electrolyte material selected from:

[0113] -Li d A 1 x A 2 y (TO4) z Garnet, of which A 1 is a cation with an oxidation degree of +II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; wherein A 2 is a cation of oxidation degree +III, preferably Al, Fe, Cr, Ga, Ti, La; wherein (TO4) is an anion, wherein T is an atom of oxidation degree +IV, located at the center of a tetrahedron formed by oxygen atoms, and wherein TO4 is preferably a silicate or zirconate anion, it being understood that all or part of the element T of oxidation degree +IV may be replaced by atoms of oxidation degree +III or +V, such as Al, Fe, As, V, Nb, In, Ta; it being understood that: d is 2 to 10, preferably 3 to 9, even more preferably 4 to 8; x is 2.6 to 3.4 (preferably 2.8 to 3.2); y is 1.7 to 2.3 (preferably 1.9 to 2.1) and z is 2.9 to 3.1;

[0114] - garnet, preferably selected from: Li7La3Zr2O 12 ;Li6La2BaTa2O 12 ;Li 5.5 La3Nb 1.75 In 0.25 O 12 ;Li5La3M2O 12 , where M = Nb or Ta or a mixture of these two compounds; Li 7-x Ba x La 3-x M2O 12 , where 0≤x≤1 and M=Nb or Ta or a mixture of these two compounds; Li 7-x La3Zr 2-x M x O 12 , where 0≤x≤2 and M=Al, Ga or Ta or a mixture of two or three of these compounds;

[0115] - lithiated phosphates, preferably selected from the following types of lithiated phosphates: NaSICON, Li3PO4; LiPO3; Li3Al 0.4 Sc 1.6 (PO4)3, called "LASP"; Li 1.2 Zr 1.9 Ca 0.1 (PO4)3;LiZr2(PO4)3;Li 1+3x Zr2(P 1-x Si x O4)3, of which 1.8 <x<2.3;Li 1+6x Zr2(P 1-x B x O4)3, where 0≤x≤0.25; Li3(Sc 2-x M x )(PO4)3, wherein M=Al or Y and 0≤x≤1; Li 1+x M x (Sc) 2-x (PO4)3, wherein M = Al, Y, Ga or a mixture of these three compounds and 0≤x≤0.8; Li 1+x M x (Ga 1-y Sc y ) 2-x (PO4)3, wherein 0≤x≤0.8; 0≤y≤1 and M=Al or Y or a mixture of these two compounds; Li 1+x M x (Ga) 2-x(PO4)3, wherein M = Al, Y or a mixture of these two compounds and 0≤x≤0.8; Li 1+x Al x Ti 2-x (PO4)3, where 0≤x≤1, is called "LATP"; or Li 1+x Al x Ge 2-x (PO4)3, where 0≤x≤1, is called "LAGP"; or Li 1+x+z M x (Ge 1-y Ti y ) 2-x Si z P 3-z O 12 wherein 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-y O 12 , wherein 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-y O 12 , wherein M=Al, Y, Ga or a mixture of these three compounds and Q=Si and / or Se, 0≤x≤0.8 and 0≤y≤1; or Li 1+x+y+z M x (Ga 1-y Sc y ) 2-x Q z P 3-z O 12 , wherein 0≤x≤0.8, 0≤y≤1, 0≤z≤0.6, wherein M=Al or Y or a mixture of these two compounds and Q=Si and / or Se; or Li 1+x Zr 2-x B x (PO4)3, where 0≤x≤0.25; or Li 1+x Zr 2-x Ca x (PO4)3, where 0≤x≤0.25; or Li 1+ x M 3 x M 2-x P3O 12, where 0 ≤ x ≤ 1 and M 3 = Cr, V, Ca, B, Mg, Bi, and / or Mo, M = Sc, Sn, Zr, Hf, Se, or Si, or a mixture of these compounds; Li 1+2x Ca x Zr 2-x (PO4)3, where 0 ≤ x ≤ 0.25;

[0116] - Lithiated borates, preferably selected from: Li3(Sc 2-x M x )(BO3)3, where M = Al or Y and 0 ≤ x ≤ 1; Li 1+x M x (Sc) 2-x (BO3)3, where M = Al, Y, Ga, or a mixture of these three compounds and 0 ≤ x ≤ 0.8; Li 1+x M x (Ga 1-y Sc y ) 2-x (BO3)3, where 0 ≤ x ≤ 0.8, 0 ≤ y ≤ 1, and M = Al or Y; Li 1+x M x (Ga) 2-x (BO3)3, where M = Al, Y, or a mixture of these two compounds and 0 ≤ x ≤ 0.8; Li3BO3, Li3BO3 - Li2SO4, Li3BO3 - Li2SiO4, Li3BO3 - Li2SiO4 - Li2SO4;

[0117] - Oxynitrides, preferably selected from Li3PO 4-x N 2x / 3 、Li4SiO 4-x N 2x / 3 、Li4GeO 4-x N 2x / 3 , where 0 < x < 4 or Li3BO 3-x N 2x / 3 , where 0 < x < 3;

[0118] - Lithiated compounds based on lithium phosphorus oxynitride, called "LiPON", in the form of Li x PO y N z where x ~ 2.8 and 2y + 3z ~ 7.8 and 0.16 ≤ z ≤ 0.4, especially Li[[ID=​​​​​​​​​​​​, where 2x+3y+2z=5=w or compound Li w PO x N y S z , wherein 3.2≤x≤3.8, 0.13≤y≤0.4, 0≤z≤0.2, 2.9≤w≤3.3 or a compound of the following form: Li t P x Al y O u N v S w , where 5x+3y=5,2u+3v+2w=5+t, 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;

[0119] - materials based on lithium phosphorus or boron oxynitride, referred to as "LiPON" and "LIBON", respectively, optionally further comprising silicon, sulfur, zirconium, aluminum, or a combination of aluminum, boron, sulfur and / or silicon and boron for materials based on lithium phosphorus oxynitride;

[0120] - Lithium, phosphorus, and silicon oxynitride-based lithiated compounds, known as "LiSiPON," especially Li 1.9 Si 0.28 P 1.0 O 1.1 N 1.0 ;

[0121] -Lithium oxynitrides of the type LiBON, LiBSO, LiSiPON, LiSON, thio-LiSiCON, LiPONB (wherein B, P, and S represent boron, phosphorus, and sulfur, respectively);

[0122] - lithium oxynitrides of the LiBSO type, for example (1-x)LiBO2-xLi2SO4, where 0.4≤x≤0.8;

[0123] - lithiated oxide, preferably selected from Li7La3Zr2O 12 or Li 5+x La3(Zr x ,A 2-x )O 12 , where A=Sc, Y, Al, Ga and 1.4≤x≤2 or Li 0.35 La 0.55 TiO3 or Li 3x La 2 / 3-x TiO3, where 0≤x≤0.16 (LLTO);

[0124] - Silicate, preferably selected from Li2Si2O5, Li2SiO3, Li2Si2O6, LiAlSiO4, Li4SiO4, LiAlSi2O6;

[0125] - Anti - perovskite solid electrolyte, selected from: Li3OA, where A is a halide or a mixture of halides, preferably selected from at least one element of the elements F, Cl, Br, I or a mixture of two or three or four of these elements; Li (3-x) M x / 2 OA, where 0 < x ≤ 3, M is a divalent metal, preferably selected from at least one element of the elements Mg, Ca, Ba, Sr or a mixture of two or three or four of these elements, A is a halide or a mixture of halides, preferably selected from at least one element of the elements F, Cl, Br, I or a mixture of two or three or four of these elements; Li (3-x) M 3 x / 3 OA, where 0 ≤ x ≤ 3, M 3 is a trivalent metal, A is a halide or a mixture of halides, preferably selected from at least one element of the elements F, Cl, Br, I or a mixture of two or three or four of these elements; or LiCOX z Y (1-z) , where X and Y are the halides mentioned above when referring to A, and 0 ≤ z ≤ 1,

[0126] - Compound La 0.51 Li 0.34 Ti 2.94 、Li 3.4 V 0.4 Ge 0.6 O4、Li2O - Nb2O5、LiAlGaSPO4;

[0127] - Formulations based on: Li2CO3, B2O3, Li2O, Al(PO3)3LiF, P2S3, Li2S, Li3N, Li 14 Zn(GeO4)4、Li 3.6 Ge 0.6 V 0.4 O4、LiTi2(PO)3、Li 3.25 Ge 0.25 P 0.25 S4、Li 1.3 Al 0.3 Ti 1.7 (PO4)3、Li 1+x Al x M 2-x (PO4)3 (where M = Ge, Ti and / or Hf, and where 0 < x <1+x+y Al x Ti 2-x Si y P 3-y O 12 (where 0≤x≤1 and 0≤y≤1).

[0128] Use of coated nanoparticles ("core-shell" type)

[0129] In general, the nanoparticles used in the inks used to create these electrode deposits can also have a core-shell structure. Indeed, the performance of the dense electrodes obtained by the methods described herein will depend on their ionic and electronic conductivity properties. Furthermore, it is important to apply a "shell" of an organic or inorganic material with good electronic and / or ionic conductivity to the surface of the active material nanoparticles.

[0130] Therefore, in a preferred embodiment, the core is formed of an electrode material (anode or cathode), and the shell is formed of a material that is both conductive and does not block the passage of lithium ions. For example, the shell can be formed of a metal layer that is thin enough to allow lithium ions to pass through, or a graphite layer that is thin enough to allow lithium ions to pass through, or an inorganic or organic layer that is an ion conductor that is also a good electron conductor.

[0131] The core-shell approach can also be applied to the manufacture of electrolytes. Thus, in another embodiment, the core of the nanoparticles used in the method of the present invention is formed by an electrolyte material, while the shell is formed by an inorganic or organic material that is a good ion (especially lithium ion) conductor and should be a good electronic insulator.

[0132] When the shell layer is an organic layer, it is preferred that this layer be made of a polymer material. Polymer layers have the advantage, inter alia, of being ductile, which contributes to the compactness of the layer deposited using these particles.

[0133] We now describe a method for preparing inorganic nanoparticles with polymer shells. This method is particularly suitable for nanoparticles of electrolyte materials, where the shell should be both an electrical insulator and an ion conductor. This method, referred to herein as "functionalizing" the core-forming inorganic nanoparticles with the shell, involves grafting molecules with a QZ-type structure onto the surface of the nanoparticles, where Q is a functional group that binds the molecule to the surface and Z is preferably a PEO group.

[0134] Via the Q group, complexing functions of nanoparticle surface cations can be used, such as phosphate or phosphonate functions.

[0135] Preferably, the inorganic nanoparticles are functionalized by PEO derivatives of the following type

[0136]

[0137] Wherein X represents an alkyl chain or a hydrogen atom,

[0138] n is between 40 and 10,000 (preferably between 50 and 200),

[0139] m is between 0 and 10, and

[0140] Q' is an embodiment of Q, representing a group selected from the group consisting of:

[0141]

[0142] wherein R represents an alkyl chain or a hydrogen atom, R′ represents a methyl group or an ethyl group, x is between 1 and 5, and x′ is between 1 and 5.

[0143] More preferably, the inorganic nanoparticles are functionalized with methoxy-PEO-phosphonate.

[0144]

[0145] wherein n is between 40 and 10,000, preferably between 50 and 200.

[0146] According to one advantageous embodiment, a solution of QZ (or Q'-Z, if applicable) is added to a colloidal suspension of electrolyte nanoparticles of an electrolyte or electronic insulator, such that the molar ratio of Q (including Q' herein) to a set of cations present in the inorganic nanoparticles (abbreviated herein as "NP-C") is 1 to 0.01, preferably 0.1 to 0.02. When the Q / NP-C molar ratio exceeds 1, the functionalization of the electronic inorganic nanoparticles by molecular QZ tends to induce spatial dimensions, making the nanoparticles incompletely functionalized; this also depends on the size of the nanoparticles. When the molar ratio Q / NP-C is less than 0.01, the amount of molecular QZ may be insufficient to provide sufficient lithium-ion conductivity; this also depends on the particle size. Using a larger amount of QZ during the functionalization process results in unnecessary QZ consumption.

[0147] Functionalization of the inorganic nanoparticles is performed using a colloidal suspension of inorganic nanoparticles at a mass concentration of 0.1% to 50%, preferably 5% to 25%, and even more preferably 10%. At high concentrations, there may be a risk of bridging and a lack of access to the surface to be functionalized (risk of particle precipitation or poor or no functionalization). Preferably, the inorganic nanoparticles are dispersed in a liquid phase (e.g., water or ethanol).

[0148] The reaction can be carried out in any suitable solvent that can dissolve the molecule QZ.

[0149] Depending on the molecule QZ, the functionalization conditions can be optimized by adjusting the reaction temperature and duration, as well as the solvent used. After adding the QZ solution to the colloidal suspension of electrolyte nanoparticles, the reaction medium is stirred for 0 to 24 hours (preferably 5 minutes to 12 hours, even more preferably 0.5 to 2 hours), so that at least a portion, and preferably all, of the QZ molecules are grafted onto the surface of the inorganic nanoparticles. Functionalization can be carried out by heating, preferably at temperatures between 20°C and 100°C. The temperature of the reaction medium must be adapted to the choice of functionalizing molecule QZ.

[0150] Thus, these functionalized nanoparticles have a core or inorganic material and a PEO shell. The shell thickness can typically be 1 nm to 100 nm; this thickness can be determined by transmission electron microscopy after labeling the polymer with ruthenium oxide (RuO4).

[0151] The nanoparticles thus functionalized are then preferably purified by successive cycles of centrifugation and redispersion and / or by tangential filtration.

[0152] After redispersion of the functionalized inorganic nanoparticles, the suspension may be reconcentrated by any suitable means until the desired dry extract is obtained.

[0153] Preferably, the dry extract of the PEO-functionalized inorganic nanoparticle suspension comprises more than 40% (by volume) of solid electrolyte material, preferably more than 60%, even more preferably more than 70% of solid electrolyte material.

[0154] Densification of the layer produced using organic core-shell nanoparticles after their deposition can be carried out in a suitable manner, preferably:

[0155] a) by any mechanical means, in particular by mechanical compression, preferably uniaxial compression;

[0156] b) by hot pressing, i.e. heat treatment under pressure. The optimal temperature is closely related to the chemical composition of the deposited material, as well as the particle size and the compactness of the layer. A controlled atmosphere is preferably maintained to prevent oxidation and surface contamination of the deposited particles.

[0157] Preferably, compression is carried out in a controlled atmosphere and at a temperature between ambient temperature and the melting point of the polymer used (usually PEO); hot pressing can be carried out at a temperature between ambient temperature (about 20°C) and about 300°C; but preferably does not exceed 200°C (or more preferably 100°C) to prevent degradation of the PEO.

[0158] As mentioned above, one of the advantages of organic shells is their ductility; PEO, for example, is a polymer that easily deforms under relatively low pressure. Therefore, densification of electrolyte nanoparticles or electronic insulator nanoparticles functionalized with polymers such as PEO can be achieved simply by mechanical compression (applying mechanical pressure). Compression is preferably performed within a pressure range between 10 MPa and 500 MPa, preferably between 50 MPa and 200 MPa, and at a temperature between 20°C and 200°C.

[0159] At the interface, PEO is amorphous, ensuring good ionic contact between solid electrolyte particles. Therefore, PEO can conduct lithium ions even in the absence of a liquid electrolyte; PEO is also an electronic insulator. This facilitates the assembly of lithium-ion batteries at low temperatures, limiting the risk of interdiffusion at the interface between electrolyte and electrode.

[0160] In lithium-ion batteries, the thickness of the electrolyte layer obtained after densification may be less than 10 μm, preferably less than 6 μm, preferably less than 5 μm, thus limiting the thickness and weight of the battery without reducing its performance.

[0161] Use of the method according to the invention for depositing a layer in a device which also comprises a mesoporous layer

[0162] The method of the present invention can deposit inorganic dense layers in electrochemical and other devices (such as lithium ion batteries). In these devices, the dense layer can perform the function of anode or cathode or electrode, and the device can include multiple inorganic dense layers of the present invention. These devices can be "all solid-state" types, and the dense layer only has very low porosity. According to a variation of the present invention, the device also includes at least one porous inorganic layer.

[0163] According to this variant of the invention, the "porous inorganic layer", preferably the mesoporous layer, can be deposited using a suspension of nanoparticle aggregates or agglomerates, preferably a concentrated suspension containing nanoparticle agglomerates, using a method preferably selected from the following: electrophoresis, printing, preferably selected from inkjet printing and flexographic printing, and coating, preferably selected from roller coating, curtain coating, doctor blade coating, slit coating, dip coating.

[0164] More specifically, the average primary diameter D of at least one inorganic material is used. 50 Colloidal suspensions of nanoparticle aggregates or agglomerates between 2 nm and 100 nm, preferably between 2 nm and 60 nm, said aggregates or agglomerates typically having an average diameter D 50The layer thus obtained is then dried and consolidated by compression and / or heating to obtain a porous layer, preferably a mesoporous inorganic layer. This method is particularly advantageous for nanoparticles formed from electrolyte materials.

[0165] The mesoporous layer can be deposited on a dense layer deposited using the method of the present invention, or the dense layer can be deposited on the mesoporous layer prepared using the method described above.

[0166] In order for the porous layer to perform its electrolyte function, it must be impregnated with a flowing cationic carrier liquid; in the case of lithium-ion batteries, the cations are lithium cations. The lithium ion carrier phase is preferably selected from the following group:

[0167] o an electrolyte consisting of at least one aprotic solvent and at least one lithium salt;

[0168] o an electrolyte consisting of at least one ionic liquid or ionic polyliquid and at least one lithium salt;

[0169] o a mixture of at least one aprotic solvent and at least one ionic liquid or ionic multi-liquid and at least one lithium salt;

[0170] o making the polymer an ion conductor by adding at least one lithium salt; and

[0171] o making polymers ionic conductors by incorporating liquid electrolytes into the polymer phase or mesoporous structure,

[0172] The polymer is preferably selected from poly(ethylene oxide), poly(propylene oxide), polydimethylsiloxane, polyacrylonitrile, poly(methyl methacrylate), poly(vinyl chloride), poly(vinylidene fluoride), PVDF-hexafluoropropylene.

[0173] Example of manufacturing a lithium-ion microbattery

[0174] Described herein is a method for fabricating a lithium-ion microbattery using the layers of the present invention.

[0175] a) Preparing electrodes using the deposition method of the present invention

[0176] The first dense Li4Ti5O 12 A second dense LiMn2O4 electrode was also deposited using a similar method.

[0177] A thinner mesoporous film of Li3PO4 agglomerates was then deposited on each of the two electrodes to serve as the separator membrane for the battery and was prepared as described below.

[0178] b) Deposition of diaphragm

[0179] Li3PO4 nanoparticle suspensions were prepared using two solutions described below. First, 45.76 g of CH3COOLi·2H2O was dissolved in 448 ml of water, and 224 ml of ethanol was then added to the medium with vigorous stirring to produce Solution A. Second, 16.24 g of H3PO4 (85 wt% aqueous solution) was diluted with 422.4 ml of water, and 182.4 ml of ethanol was added to this solution to produce a second solution, hereinafter referred to as Solution B. Solution B was then added to Solution A with vigorous stirring.

[0180] In the Ultraturrax that homogenizes the medium TM The resulting solution (which became completely transparent after the bubbles formed during mixing disappeared) was added to 4.8 liters of acetone using a homogenizer. A white precipitate was immediately observed suspended in the liquid phase.

[0181] The reaction medium is homogenized for 5 minutes and then maintained under magnetic stirring for 10 minutes. The whole is allowed to stand for 1 to 2 hours. The supernatant is discarded, and the remaining suspension is centrifuged at 6000g for 10 minutes. 1.2 liters of water are then added to resuspend the precipitate (using a sonotrode and magnetic stirring). This type of washing is then repeated two more times with ethanol. Under vigorous stirring, 15 ml of a 1 g / ml bis(2-(methacryloyloxy)ethyl)phosphate solution is added to the resulting ethanolic colloidal suspension. This stabilizes the suspension. The suspension is then sonicated using a sonotrode. The suspension is then centrifuged at 6000g for 10 minutes. The precipitate is then redispersed in 1.2 liters of ethanol and centrifuged at 6000g for 10 minutes. The resulting precipitate is redispersed in 900 ml of ethanol to obtain a 15 g / l suspension suitable for electrophoretic deposition.

[0182] Thus, an ethanolic suspension of approximately 200 nm aggregates consisting of 10 nm primary Li3PO4 particles was obtained.

[0183] A thin, porous layer of Li3PO4 was then electrophoretically deposited on the previously prepared anode and cathode surfaces by applying an electric field of 20 V / cm to the previously obtained suspension of Li3PO4 nanoparticles for 90 seconds, obtaining a layer of approximately 2 μm. This layer was then air-dried at 120°C, followed by a calcination treatment at 350°C for 120 minutes to remove any traces of organic residues.

[0184] c) Assembly of electrodes and separators

[0185] In each previously prepared electrode (Li 1+x Mn2-y O4 and Li4Ti5O 12 After depositing 2 μm porous Li3PO4 on the substrate, the two subsystems were stacked so that the Li3PO4 films were in contact with each other. The stack was then hot-pressed between two flat plates in a vacuum. To do this, the stack was first placed under a pressure of 5 MPa and then at 10 -3 The stack was then hot-pressed at 550°C for 20 minutes under a pressure of 45 MPa, followed by drying in vacuum at 10 mbar for 30 minutes. The press plate was then heated to 550°C at a rate of 0.4°C / s. The stack was then hot-pressed at 550°C for 20 minutes under a pressure of 45 MPa, after which the system was cooled to ambient temperature. The assembly was then dried in vacuum at 120°C for 48 hours.

[0186] d) Using liquid electrolyte to impregnate the diaphragm

[0187] The assembly was then impregnated in an anhydrous atmosphere by immersing it in an electrolyte solution containing PYR14TFSI and 0.7M LiTFSI. PYR14TFSI is the standard abbreviation for 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide. LITFSI is the standard abbreviation for lithium bis(trifluoromethanesulfonyl)imide (CAS No. 90076-65-6). This ionic liquid enters the pores of the separator instantaneously via capillary action. Each end of the system was kept immersed in a drop of the electrolyte mixture for 5 minutes.

[0188] It is worth noting that in industrial manufacturing methods, impregnation is performed after encapsulation of the battery and then the electrical contact elements are produced.

[0189] Generally, the battery of the present invention can be a lithium-ion microbattery. In particular, the battery can be designed and dimensioned to have a capacitance of less than or equal to about 1 mAh (commonly referred to as a "microbattery"). Typically, microbatteries are designed to be compatible with microelectronics manufacturing methods.

[0190] These microbatteries can be produced as follows:

[0191] - having only layers according to the invention of the "all-solid" type, ie without an impregnated liquid or paste phase (the liquid or paste phase being optionally a lithium-ion conducting medium capable of acting as an electrolyte),

[0192] - or having an electrode according to the invention and a mesoporous "all-solid" type separator, impregnated with a liquid or paste phase, usually a lithium-ion conducting medium, which spontaneously enters the interior of the layer and no longer exits it, so that the layer can be considered as quasi-solid,

[0193] - or having an electrode according to the invention and an impregnated porous separator (ie a layer having an open pore network, which can be impregnated with a liquid or paste phase so that these layers have wet properties).

[0194] Different aspects of the invention

[0195] From the description given it is apparent that the invention has several aspects, features and combinations of features which are compiled in a summarized manner hereinafter.

[0196] A first aspect of the present invention is a method for manufacturing a dense layer, comprising the following steps:

[0197] - providing a substrate and providing a suspension of non-aggregated nanoparticles of an inorganic material P,

[0198] - depositing a layer on said substrate using a suspension of primary nanoparticles of material P;

[0199] - drying the resulting layer,

[0200] - densification of the dried layer by mechanical compression and / or heat treatment,

[0201] It should be understood that the third and fourth steps can be performed at least partially simultaneously, or at elevated temperatures.

[0202] The method is characterized in that the suspension of non-aggregated nanoparticles of material P comprises nanoparticles of material P having a distribution of particle sizes, the particle sizes being 50 Value representation, thus:

[0203] The particle size distribution includes nanoparticles of the material P having a first particle size D1 between 20 nm and 50 nm, and nanoparticles of the material P having a second particle size D2, wherein the second particle size D2 has a particle size D 50 At least five times smaller than D1.

[0204] According to an alternative, the distribution has nanoparticles of material P having a mean size of less than 50 nm and a ratio of the standard deviation to the mean size greater than 0.6.

[0205] According to a first variant of this first aspect, the suspension of non-aggregated nanoparticles of material P comprises nanoparticles of material P having a first particle size D1 between 20 nm and 50 nm and nanoparticles of material P having a second particle size D2, characterized in that: the second particle size D2 50 The value is at least five times smaller than D1, and particles of particle size D1 account for 50% to 75% of the total mass of the nanoparticles. Preferably, the average diameter of the second nanoparticle population is at least one-fifteenth, preferably at least one-twelfth, of the average diameter of the first nanoparticle population.

[0206] According to a second variant of this first aspect, which is also compatible with its first variant, the suspension of non-aggregated nanoparticles of material P is obtained using a monodisperse suspension of nanoparticles of particle size D1 .

[0207] According to a third variant of this first aspect, which is also compatible with its first and second variants, the suspension of nanoparticles of particle size D2 is obtained using a monodisperse suspension.

[0208] According to a fourth variant of this first aspect, which is also compatible with the first, second and third variants thereof, a mixture of two nanoparticle size populations is used, whereby the mean diameter of the largest distribution does not exceed 100 nm, preferably does not exceed 50 nm. Preferably, the first largest nanoparticle population is σ / R 平均值 The particle size distribution characterized by the ratio is less than 0.6.

[0209] In a first sub-variation of this variation, preferably the largest population of nanoparticles constitutes 50% to 75% of the dry extract of the sediment and the second population of nanoparticles constitutes 50% to 25% of the dry extract of the sediment (these percentages are expressed as mass percentages relative to the total mass of nanoparticles in the sediment).

[0210] In a second sub-variation of the fourth variation, the average diameter of the second nanoparticle population is at least 5 times smaller than the average diameter of the first nanoparticle population, and preferably the average diameter of the second nanoparticle population is at least one-fifteenth, preferably at least one-twelfth, of the first nanoparticle population. Preferably, the second nanoparticle population is σ / R 平均值 The particle size distribution characterized by the ratio is less than 0.6.

[0211] According to a fifth variant of the first aspect, which is also compatible with its first, second, third and fourth variants, a method is used to deposit the dense layer, selected from printing (in particular inkjet printing and flexographic printing), electrophoresis and coating (in particular roller coating, curtain coating, doctor blade coating, dip coating or slot coating).

[0212] According to a sixth variant of the first aspect, which is also compatible with the first, second, third, fourth and fifth variants thereof, the viscosity of the suspension measured at 20° C. is between 20 cP and 2000 cP.

[0213] According to a seventh variant of this first aspect, which is also compatible with its first, second, third, fourth, fifth and sixth variants, said material P is an inorganic material, preferably chosen from the group formed by:

[0214] - cathode material, preferably selected from the group formed by:

[0215] -oxide LiMn2O4, Li1+x Mn 2-x O4, where 0 < x < 0.15, LiCoO2, LiNiO2, LiMn 1.5 Ni 0.5 O4, LiMn 1.5 Ni 0.5-x X x O4, where X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earth elements Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, where 0 < x < 0.1, LiMn 2-x M x O4, where M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg or a mixture of these compounds, where 0 < x < 0.4, LiFeO2, LiMn 1 / 3 Ni 1 / 3 Co 1 / 3 O2, LiNi 0.8 Co 0.15 Al 0.05 O2, LiAl x Mn 2-x O4, where 0 ≤ x < 0.15, LiNi 1 / x Co 1 / y [[ID=?]] 1 / z [[ID=?]]O2, where x + y + z = 10;

[0216] - Phosphates LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2(PO4)3; phosphates of the formula LiMM’PO4, where M and M’ (M ≠ M’) are selected from Fe, Mn, Ni, Co, V;

[0217] - All lithiated forms of the following chalcogenides: V2O5, V3O8, TiS2, titanium oxysulfide (TiO y S z S, where z = 2 - y and 0.3 ≤ y ≤ 1), tungsten oxysulfide (WO y S z S, where 0.6 < y < 3 and 0.1 < z < 2), CuS, CuS2, preferably Li<00003?]] x V2O5, where 0 < x ≤ 2, LixV3O8, where 0 < x ≤ 1.7, Li x TiS2, where​​​​​​​​​​​z , Li x CuS, Li x CuS2;

[0218] - Anode material, preferably selected from the group formed by:

[0219] - Carbon nanotubes, graphene, graphite;

[0220] - Lithiated iron phosphate (typical molecular formula LiFePO4);

[0221] - Mixed silicon tin oxynitride (typical molecular formula Si a Sn b O y N z , where a > 0, b > 0, a + b ≤ 2, 0 < y ≤ 4, 0 < z ≤ 3) (also known as SiTON), especially SiSn 0.87 O 1.2 N 1.72 ; and the oxynitride - carbide of the typical molecular formula Si a Sn b C c O<o:p>N z where a > 0, b > 0, a + b ≤ 2, 0 < c < 10, 0 < y < 24, 0 < z < 17;

[0222] - Nitrides of the following types: Si x N y (especially where x = 3 and y = 4), Sn x N y (especially where x = 3 and y = 4), Zn x N y (especially where x = 3 and y = 2), Li 3-x M x N (where 0 ≤ x ≤ 0.5 when M = Co, 0 ≤ x ≤ 0.6 when M = Ni, 0 ≤ x ≤ 0.3 when M = Cu); Si 3-x M x N4, where M = Co or Fe and 0 ≤ x ≤ 3,

[0223] - Oxides SnO2, SnO, Li2SnO3, SnSiO3, Li x SiO y (x >= 0 and 2 > y > 0), Li4Ti5O 12 , TiNb2O7, Co3O4, SnB 0.6 P 0.4 O 2.9 and TiO2,

[0224] - a complex oxide TiNb2O7 containing 0 to 10% by mass of carbon, preferably selected from graphene and carbon nanotubes;

[0225] - an electrolyte material, preferably selected from the group formed by:

[0226] -Li d A 1 x A 2 y (TO4) z Garnet, of which A 1 is a cation with an oxidation degree of +II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; wherein A 2 is a cation of oxidation degree +III, preferably Al, Fe, Cr, Ga, Ti, La; wherein (TO4) is an anion, wherein T is an atom of oxidation degree +IV, located at the center of a tetrahedron formed by oxygen atoms, and wherein TO4 is preferably a silicate or zirconate anion, it being understood that all or part of the element T of oxidation degree +IV may be replaced by atoms of oxidation degree +III or +V, for example Al, Fe, As, V, Nb, In, Ta; it being understood that: d is 2 to 10, preferably 3 to 9, even more preferably 4 to 8; x is 2.6 to 3.4 (preferably 2.8 to 3.2); y is 1.7 to 2.3 (preferably 1.9 to 2.1) and z is 2.9 to 3.1;

[0227] - garnet, preferably selected from: Li7La3Zr2O 12 ;Li6La2BaTa2O 12 ;Li 5.5 La3Nb 1.75 In 0.25 O 12 ;Li5La3M2O 12 , where M = Nb or Ta or a mixture of these two compounds; Li 7-x Ba x La 3-x M2O 12 , where 0≤x≤1 and M=Nb or Ta or a mixture of these two compounds; Li 7-x La3Zr 2-x M x O 12 , where 0≤x≤2 and M=Al, Ga or Ta or a mixture of two or three of these compounds;

[0228] - lithiated phosphates, preferably selected from the following types of lithiated phosphates: NaSICON, Li3PO4; LiPO3; Li3Al 0.4 Sc1.6 (PO4)3, called "LASP"; Li 1.2 Zr 1.9 Ca 0.1 (PO4)3;LiZr2(PO4)3;Li 1+3x Zr2(P 1-x Si x O4)3, of which 1.8 <x<2.3;Li 1+6x Zr2(P 1-x B x O4)3, where 0≤x≤0.25; Li3(Sc 2-x M x )(PO4)3, wherein M=Al or Y and 0≤x≤1; Li 1+x M x (Sc) 2-x (PO4)3, wherein M = Al, Y, Ga or a mixture of these three compounds and 0≤x≤0.8; Li 1+x M x (Ga 1-y Sc y ) 2-x (PO4)3, wherein 0≤x≤0.8; 0≤y≤1 and M=Al or Y or a mixture of these two compounds; Li 1+x M x (Ga) 2-x (PO4)3, wherein M = Al, Y or a mixture of these two compounds and 0≤x≤0.8; Li 1+x Al x Ti 2-x (PO4)3, where 0≤x≤1, is called "LATP"; or Li 1+x Al x Ge 2-x (PO4)3, where 0≤x≤1, is called "LAGP"; or Li 1+x+z M x (Ge 1-y Ti y ) 2-x Si z P 3-z O 12 , wherein 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-y O 12 , wherein M=Al and / or Y and Q=Si and / or Se, 0≤x≤0.8 and 0≤y≤1; or Li1+x+y M x Sc 2-x Q y P 3-y O 12 , wherein M=Al, Y, Ga or a mixture of these three compounds and Q=Si and / or Se, 0≤x≤0.8 and 0≤y≤1; or Li 1+x+y+z M x (Ga 1-y Sc y ) 2-x Q z P 3-z O 12 , wherein 0≤x≤0.8, 0≤y≤1, 0≤z≤0.6, wherein M=Al or Y or a mixture of these two compounds and Q=Si and / or Se; or Li 1+x Zr 2-x B x (PO4)3, where 0≤x≤0.25; or Li 1+x Zr 2-x Ca x (PO4)3, where 0≤x≤0.25; or Li 1+ x M 3 x M 2-x P3O 12 , where 0≤x≤1 and M 3 =Cr, V, Ca, B, Mg, Bi and / or Mo, M = Sc, Sn, Zr, Hf, Se or Si, or a mixture of these compounds; Li 1+2x Ca x Zr 2-x (PO4)3, where 0≤x≤0.25;

[0229] -lithiated borates, preferably selected from: Li3(Sc 2-x M x )(BO3)3, wherein M=Al or Y and 0≤x≤1; Li 1+x M x (Sc) 2-x (BO3)3, wherein M = Al, Y, Ga or a mixture of these three compounds and 0≤x≤0.8; Li 1+x M x (Ga 1-y Sc y ) 2-x (BO3)3, wherein 0≤x≤0.8, 0≤y≤1 and M=Al or Y; Li 1+x M x (Ga) 2-x(BO3)3, where M = Al, Y or a mixture of these two compounds and 0 ≤ x ≤ 0.8; Li3BO3, Li3BO3-Li2SO4, Li3BO3-Li2SiO4, Li3BO3-Li2SiO4-Li2SO4;

[0230] - Oxynitrides, preferably selected from Li3PO 4-x N 2x / 3 、Li4SiO 4-x N 2x / 3 、Li4GeO 4-x N 2x / 3 ,where 0 < x < 4 or Li3BO 3-x N 2x / 3 ,where 0 < x < 3;

[0231] - Lithiated compounds based on lithium phosphorus oxynitrides, called "LiPON", in the form of Li x PO y N z where x ~ 2.8 and 2y + 3z ~ 7.8 and 0.16 ≤ z ≤ 0.4, especially Li 2.9 PO 3.3 N 0.46 ,but also the compound Li w PO x N y S z ,where 2x + 3y + 2z = 5 = w or the compound Li w PO x N y S z ,where 3.2 ≤ x ≤ 3.8, 0.13 ≤ y ≤ 0.4, 0 ≤ z ≤ 0.2, 2.9 ≤ w ≤ 3.3 or compounds of the following form: Li t P x Al y O u N v S w [[ID=6Z]],where 5x + 3y = 5, 2u + 3v + 2w = 5 + t, 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;

[0232] - Materials based on lithium phosphorus or boron oxynitrides, called "LiPON" and "LIBON" respectively, optionally further containing silicon, sulfur, zirconium, aluminum or a combination of aluminum, boron, sulfur and / or silicon and boron, for materials based on lithium phosphorus oxynitrides;

[0233] - Lithiated compounds based on lithium, phosphorus and silicon oxynitrides, called "LiSiPON", especially Li 1.9Si 0.28 P 1.0 O 1.1 N 1.0 ;

[0234] - Lithium oxynitrides of the LiBON, LiBSO, LiSiPON, LiSON, thio-LiSiCON, LiPONB type, where B, P, and S represent boron, phosphorus, and sulfur, respectively;

[0235] - Lithium oxynitrides of the LiBSO type, such as (1 - x)LiBO2 - xLi2SO4, where 0.4 ≤ x ≤ 0.8;

[0236] - Lithiated oxides, preferably selected from Li7La3Zr2O 12 or Li 5+x La3(Zr x ,A 2-x )O 12 , where A = Sc, Y, Al, Ga and 1.4 ≤ x ≤ 2 or Li 0.35 La 0.55 TiO3 or Li 3x La 2 / 3-x TiO3, where 0 ≤ x ≤ 0.16 (LLTO);

[0237] - Silicates, preferably selected from Li2Si2O5, Li2SiO3, Li2Si2O6, LiAlSiO4, Li4SiO4, LiAlSi2O6;

[0238] - Perovskite - type solid electrolytes selected from: Li3OA, where A is a halide or a mixture of halides, preferably at least one of the elements F, Cl, Br, I or a mixture of two or three or four of these elements; Li (3-x) M x / 2 OA, where 0 < x ≤ 3, M is a divalent metal, preferably at least one of the elements Mg, Ca, Ba, Sr or a mixture of two or three or four of these elements, A is a halide or a mixture of halides, preferably at least one of the elements F, Cl, Br, I or a mixture of two or three or four of these elements; Li (3-x) M 3 x / 3 OA, where 0 ≤ x ≤ 3, M 3 is a trivalent metal, A is a halide or a mixture of halides, preferably at least one of the elements F, Cl, Br, I or a mixture of two or three or four of these elements; or LiCOX z Y (1-z) , where X and Y are the halides mentioned above when referring to A, and 0 ≤ z ≤ 1,

[0239] -Compound La 0.51 Li 0.34 Ti 2.94 、Li 3.4 V 0.4 Ge 0.6 O4, Li2O-Nb2O5, LiAlGaSPO4;

[0240] - Formulations based on: Li2CO3, B2O3, Li2O, Al(PO3)3LiF, P2S3, Li2S, Li3N, Li 14 Zn(GeO4)4、Li 3.6 Ge 0.6 V 0.4 O4、LiTi2(PO4)3、Li 3.25 Ge 0.25 P 0.25 S4, Li 1.3 Al 0.3 Ti 1.7 (PO4)3、Li 1+x Al x M 2-x (PO4)3 (wherein M = Ge, Ti and / or Hf, and where 0 <x<1)、Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (where 0≤x≤1 and 0≤y≤1).

[0241] According to the eighth variation of the first aspect, which is also compatible with the first, second, third, fourth, fifth, sixth and seventh variations thereof, the nanoparticles of the inorganic material P include nanoparticles consisting of a core and a shell, the core being formed by the inorganic material P and the shell being formed by another material, preferably an organic material, and even more preferably a polymer material.

[0242] In a first sub-variation of this eighth variation, the shell is formed from a material that is an electron conductor.

[0243] In a second sub-variant of this eighth variant, the shell is formed from a material that is an electronic insulator and a cation conductor, in particular a lithium ion conductor.

[0244] In a third sub-variant of this eighth variant, the shell is formed from a material that is an electron conductor and a cation conductor, in particular a lithium ion conductor.

[0245] According to a ninth variant of this first aspect, which is also compatible with the first, second, third, fourth, fifth, sixth, seventh and eighth variants, the nanoparticles of the inorganic material P (or, in the case of the eighth variant, the core is made of the inorganic material P of the nanoparticles) are prepared by precipitation in a suspension.

[0246] The second aspect of the present invention is a method for manufacturing at least one dense layer in a lithium-ion battery, wherein the method for manufacturing the dense layer is the method described in the first aspect of the present invention (including all variations and all sub-variations described in the first aspect of the present invention).

[0247] According to a first variant of this second aspect, the material P is selected so that the dense layer can be used as an anode of a lithium-ion battery.

[0248] According to a second variant of this second aspect, the material P is selected so that the dense layer can be used as a cathode for a lithium-ion battery.

[0249] According to a third variant of this second aspect, which is also compatible with the first and second variants of the second aspect, the material P is chosen so that the dense layer can be used as an electrolyte for a lithium-ion battery.

[0250] The third aspect of the present invention is a method for manufacturing at least one dense layer in a lithium-ion battery, wherein the dense layer can be obtained by the method described in the first aspect of the present invention (including all variations and all sub-variations described in the first aspect of the present invention).

[0251] According to a first variant of this third aspect, the material P is selected so that the dense layer can be used as an anode of a lithium-ion battery.

[0252] According to a second variant of this third aspect, which is also compatible with the first variant thereof, the material P is chosen so that the dense layer can be used as a cathode for a lithium-ion battery.

[0253] According to a third variant of this third aspect, which is also compatible with its first and second variants, the material P is chosen so that the dense layer can be used as an electrolyte for a lithium-ion battery.

[0254] The fourth aspect of the present invention is a method for manufacturing a lithium-ion battery, wherein the battery comprises at least one dense electrode layer deposited by the method described in the first aspect of the invention (including all variations and all sub-variations described in the first aspect of the invention), wherein a porous layer intended to form a separator is also deposited, preferably using the electrolyte material described in the seventh variation of the first aspect of the invention.

[0255] According to a first variant of this fourth aspect, the porous layer is a mesoporous layer, preferably with a mesopore volume of 25% to 75%, even more preferably 30% to 60%.

[0256] According to the second variant of this fourth aspect, which is also compatible with its first variant, the method for depositing the porous layer is preferably a method selected from the following group: electrophoresis, a printing method preferably selected from inkjet printing and flexographic printing, and a coating method preferably selected from roller coating, curtain coating, doctor blade coating, slit coating, and dip coating, it being understood that in any case, deposition is carried out using a suspension of nanoparticle aggregates or agglomerates.

[0257] According to a third variant of this fourth aspect, which is also compatible with the first and second variants thereof, the porous layer is deposited using a concentrated suspension comprising agglomerates of nanoparticles.

[0258] According to a fourth variant of this fourth aspect, which is also compatible with the first, second and third variants thereof, a material having an average primary diameter D of at least one inorganic material is used. 50 The porous layer is deposited as a colloidal suspension of aggregates or agglomerates of nanoparticles between 2 nm and 100 nm, preferably between 2 nm and 60 nm, said aggregates or agglomerates generally having an average diameter D 50 Between 50 nm and 300 nm (preferably between 100 nm and 200 nm).

[0259] According to a fifth variant of this fourth aspect, which is also compatible with the first, second, third and fourth variants thereof, the layer thus obtained is dried and consolidated by compression and / or heating to obtain a porous layer, preferably a mesoporous inorganic layer.

[0260] According to a sixth variant of this fourth aspect, which is also compatible with the first, second, third, fourth and fifth variants thereof, the porous layer is deposited on the dense layer.

[0261] According to a seventh variant of this fourth aspect, which is also compatible with the first, second, third, fourth, fifth and sixth variants thereof, the dense layer is deposited on the mesoporous layer.

[0262] According to an eighth variant of this fourth aspect, which is also compatible with the first, second, third, fourth, fifth, sixth and seventh variants thereof, a second electrode layer is deposited on the porous layer.

[0263] According to a first sub-variation of the eighth variation, the second electrode layer is a dense electrode deposited by the method described in the first aspect of the present invention.

[0264] According to the second sub-variation of the eighth variation, the second electrode layer is a porous electrode, preferably prepared according to the porous diaphragm layer preparation method related to the fourth aspect of the present invention, especially according to its first, second, third, fourth and fifth variations, and the diaphragm material is replaced by a suitable electrode material, preferably using the anode material or cathode material described in the seventh variation of the first aspect of the present invention.

[0265] According to a ninth variation of the fourth aspect, which is also compatible with the first, second, third, fourth, fifth, sixth, seventh and eighth variations thereof, the porous separator layer is impregnated with a mobile lithium ion carrier fluid, preferably selected from the group consisting of:

[0266] o an electrolyte consisting of at least one aprotic solvent and at least one lithium salt;

[0267] o an electrolyte consisting of at least one ionic liquid or ionic multi-liquid and at least one lithium salt;

[0268] o a mixture of at least one aprotic solvent and at least one ionic liquid or ionic multi-liquid and at least one lithium salt;

[0269] o making the polymer an ion conductor by adding at least one lithium salt; and

[0270] o making polymers ionic conductors by incorporating liquid electrolytes into the polymer phase or mesoporous structure,

[0271] The polymer is preferably selected from poly(ethylene oxide), poly(propylene oxide), polydimethylsiloxane, polyacrylonitrile, poly(methyl methacrylate), poly(vinyl chloride), poly(vinylidene fluoride), PVDF-hexafluoropropylene.

[0272] The fifth aspect of the present invention is a dense layer obtainable by the method described in the first aspect of the present invention, including all variations and sub-variations described in the first aspect of the present invention.

[0273] According to a first variant of this fifth aspect, the material P is selected so that the dense layer can be used as an anode of a lithium-ion battery.

[0274] According to a second variant of this fifth aspect, which is also compatible with the first variant thereof, the material P is chosen so that the dense layer can be used as a cathode for a lithium-ion battery.

[0275] According to a third variant of this fifth aspect, which is also compatible with its first and second variants, the material P is chosen so that the dense layer can be used as an electrolyte for a lithium-ion battery.

[0276] According to the fourth variation of the fifth aspect, which is also compatible with the first, second and third variations thereof, the density of the dense layer is at least 90% of the theoretical density, preferably at least 95% of the theoretical density, even more preferably at least 96% of the theoretical density, and most preferably at least 97% of the theoretical density.

[0277] The sixth aspect of the present invention is a dense layer of a lithium-ion battery obtainable by the method described in the first aspect of the present invention, including all variations and sub-variations described in the first aspect of the present invention.

[0278] According to a first variant of this sixth aspect, the material P is selected so that the dense layer can be used as an anode of a lithium-ion battery.

[0279] According to a second variant of this sixth aspect, which is also compatible with the first variant thereof, the material P is chosen so that the dense layer can be used as a cathode for a lithium-ion battery.

[0280] According to a third variant of this sixth aspect, which is also compatible with its first and second variants, the material P is chosen so that the dense layer can be used as an electrolyte for lithium-ion batteries.

[0281] The seventh aspect of the present invention is a lithium-ion battery with a capacitance not exceeding 1 mA h, referred to herein as a "microbattery", which includes the fifth aspect of the present invention, including the dense layer described in all variations and all sub-variations of the fifth aspect of the present invention.

[0282] According to a first variant of this seventh aspect, the microbattery comprises an anode which is a dense layer according to the fifth aspect of the invention.

[0283] According to a second variant of this seventh aspect, the microbattery comprises a cathode which is the dense layer according to the fifth aspect of the invention.

[0284] According to a third variant of this seventh aspect, the microbattery comprises an anode and a cathode, the anode and the cathode being the dense layers described in the fifth aspect of the invention.

[0285] According to a fourth variant of the seventh aspect, the microbattery comprises an anode, a cathode and an electrolyte, wherein the anode, the cathode and the electrolyte are the dense layers described in the fifth aspect of the invention.

[0286] According to a fourth variant of this seventh aspect, which is also compatible with the first, second and third variants thereof, the microbattery comprises a separator which is a porous layer as described in the fourth aspect of the invention.

Claims

1. A method for manufacturing a dense layer, comprising the following steps: (i) providing a substrate and providing a suspension of non-aggregated nanoparticles of material P; (ii) depositing a layer on the substrate using a suspension of primary nanoparticles of material P; (iii) drying the resulting layer; (iv) densifying the dried layer by mechanical compression and / or heat treatment, wherein steps (iii) and (iv) can be carried out at least partially simultaneously, or during a temperature increase process; The method is characterized in that the suspension of non-aggregated nanoparticles of material P comprises nanoparticles of material P having a particle size distribution, wherein the particle size is 50 Value representation, thus: - the distribution comprises nanoparticles of material P of a first particle size D1 between 20 nm and 50 nm, and nanoparticles of material P of a second particle size D2, characterized in that the second particle size D2 50 At least five times smaller than D1, with particles of size D1 constituting 50% to 75% of the total mass of the nanoparticles; or The distribution has nanoparticles of material P with a mean size of less than 50 nm and a ratio of the standard deviation to the mean size of greater than 0.

6.

2. The method according to claim 1 , wherein the suspension of non-aggregated nanoparticles of material P comprises nanoparticles of material P having a first particle size D1 between 20 nm and 50 nm and nanoparticles of material P having a second particle size D2, characterized in that: The second particle size D2 50 The value is at least five times smaller than that of D1, and particles with particle size D2 account for 50% to 25% of the total mass of nanoparticles.

3. The method according to claim 1 or 2, wherein the suspension of non-aggregated nanoparticles of material P comprises nanoparticles of material P having a first particle size D1 between 20 nm and 50 nm and nanoparticles of material P having a second particle size D2, characterized in that The second particle size D2 50 At least five times smaller than D1, and the average diameter of the nanoparticles of the second particle size is at least one-fifteenth the average diameter of the nanoparticles of the first particle size.

4. The method according to claim 3, characterized in that The average diameter of the second size nanoparticles is at least one twelfth the average diameter of the first size nanoparticles.

5. The method according to claim 1 or 2, characterized in that A suspension of non-aggregated nanoparticles of said material P is obtained using a monodisperse suspension of particle size D1 , the ratio of the standard deviation to the mean size of the nanoparticles of material P being less than 0.

6.

6. The method according to claim 1 or 2, characterized in that A suspension of nanoparticles of particle size D2 is obtained using a monodisperse suspension, the ratio of the standard deviation to the mean size of the nanoparticles of material P being less than 0.

6.

7. The method according to claim 1 or 2, characterized in that The deposition of the layers is carried out by electrophoresis, dip coating, inkjet printing, roller coating, curtain coating or doctor blade coating.

8. The method according to claim 1 or 2, characterized in that The viscosity of the suspension measured at 20°C is between 20 cP and 2000 cP.

9. The method according to claim 1 or 2, characterized in that The material P is an inorganic material.

10. The method according to claim 1 or 2, characterized in that The material P is an inorganic material selected from the group consisting of: - Oxide LiMn2O4, Li 1+x Mn 2-x O4, where 0 < x < 0.15, LiCoO2, LiNiO2, LiMn 1.5 Ni 0.5 O4, LiMn 1.5 Ni 0.5-x X x O4, where X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earth elements Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, where 0 < x < 0.1, LiMn 2-x M x O4, where M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg, or mixtures thereof, where 0 < x < 0.4, LiFeO2, LiMn 1 / 3 Ni 1 / 3Co 1 / 3 O2, LiNi 0.8 Co 0.15 Al 0.05 O2, LiAl x Mn 2-x O4, where 0 ≤ x < 0.15, LiNi 1 / x Co 1 / y Mn 1 / z O2, where x+y+z = 10; - phosphates LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2(PO4)3, LiMM'PO4, where M and M' are selected from Fe, Mn, Ni, Co, V and M is different from M'; - All lithiated forms of the following chalcogenides: V2O5, V3O8, TiS2, titanium oxysulfide TiO y S z , where z=2-y and 0.3 ≤y ≤ 1, tungsten oxysulfide WO y S z , where 0.6 < y < 3 and 0.1 < z < 2, CuS, CuS2; - Carbon nanotubes, graphene, graphite; - Lithium iron phosphate LiFePO4; - Mixed silicon tin oxynitride Si a Sn b O y N z , where a > 0, b > 0, a + b ≤ 2, 0 < y ≤ 4, 0 < z ≤ 3, is called SiTON; and Si a Sn b C c O y N z oxynitride-carbide, where a > 0, b > 0, a + b ≤ 2, 0 < c < 10, 0 < y < 24, 0 < z < 17; - Nitrides of the following types: Si x N y , where x=3 and y=4; Sn x N y , where x=3 and y=4; Zn x N y , where x=3 and y=2; Li 3-x M x N, where M=Co: 0 ≤ x ≤ 0.5, M=Ni: 0 ≤ x ≤ 0.6, M=Cu: 0 ≤ x ≤ 0.3; Si 3-x M x N4, where M = Co or Fe and 0 ≤ x ≤ 3, - Oxides SnO2, SnO, Li2SnO3, SnSiO3, Li x SiO y , where x >= 0 and 2 > y > 0, Li4Ti5O 12 、TiNb2O7、Co3O4、SnB 0.6 P 0.4 O 2.9 and TiO2, - a complex oxide TiNb2O7 containing 0 to 10% by mass of carbon; - Style Li d A 1 x A 2 y (TO4) z Garnet, of which A 1 It is a cation with oxidation degree +II, including Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; among them A 2 is a cation of oxidation degree +III, including Al, Fe, Cr, Ga, Ti, La; wherein TO4 is an anion, wherein T is an atom of oxidation degree +IV, located at the center of a tetrahedron formed by oxygen atoms, and wherein TO4 is a silicate or zirconate anion, wherein all or part of the element T of oxidation degree +IV can be replaced by atoms of oxidation degree +III or +V, including Al, Fe, As, V, Nb, In, Ta; d is 2 to 10; x is 2.6 to 3.4; y is 1.7 to 2.3 and z is 2.9 to 3.1; - Garnet, selected from: Li7La3Zr2O 12 ;Li6La2BaTa2O 12 ;Li 5.5 La3Nb 1.75 In 0.25 O 12 ;Li5La3M2O 12 , where M = Nb or Ta or a mixture of these two compounds; Li 7-x Ba x La 3-x M2O 12 , where 0 ≤ x ≤ 1 and M = Nb or Ta or a mixture of these two compounds; Li 7-x La3Zr 2-x M x O 12 , where 0 ≤ x ≤ 2 and M = Al, Ga or Ta or a mixture of two or three of these compounds; - lithiated phosphates; - Lithiated borates; - Oxynitrides; - Lithium phosphorus oxynitride-based lithiated compounds, called "LiPON", selected from Li x PO y N z , where x = 2.8, 2y+3z = 7.8 and 0.16 ≤ z ≤ 0.4, Li w PO x N y S z , where 2x+3y+2z = 5 = w or Li w PO x N y S z , where 3.2 ≤ x ≤ 3.8, 0.13 ≤ y ≤ 0.4, 0 ≤ z ≤ 0.2, 2.9 ≤ w ≤ 3.3 or Li t P x Al y O u N v S w , where 5x+3y=5, 2u+3v+2w=5+t, 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; - Lithium phosphorus or boron oxynitride based materials, referred to as "LiPON" and "LIBON", respectively, containing silicon, sulfur, zirconium, aluminum, or a combination of aluminum, boron, sulfur and / or silicon and boron for lithium phosphorus oxynitride based materials; - Lithium, phosphorus, and silicon oxynitride-based lithiated compounds, known as "LiSiPON," including Li 1.9 Si 0.28 P 1.0 O 1.1 N 1.0 ; -Lithium oxynitrides of the type LiBON, LiBSO, LiSiPON, LiSON, thio-LiSiCON, LiPONB, where B, P, and S represent boron, phosphorus, and sulfur, respectively; -LiBSO type lithium oxynitride, including (1-x)LiBO2-xLi2SO4, where 0.4≤x≤0.8; - lithiated oxides; - silicates; - The antiperovskite solid electrolyte is selected from: Li3OA, wherein A is a halide or a halide mixture, including at least one element selected from F, Cl, Br, I or a mixture of two, three or four of these elements; Li (3-x) M x / 2 OA, wherein 0< x ≤ 3, M is a divalent metal including at least one element selected from Mg, Ca, Ba, Sr, or a mixture of two, three, or four of these elements, A is a halide or a halide mixture including at least one element selected from F, Cl, Br, I, or a mixture of two, three, or four of these elements; Li (3-x) M 3 x / 3 OA, where 0≤x≤3, M 3 is a trivalent metal, A is a halide or a halide mixture comprising at least one element selected from F, Cl, Br, I or a mixture of two, three or four of these elements; or LiCOX z Y (1-z) , wherein X and Y are the halides mentioned above with respect to A, and 0 ≤ z ≤ 1, - Compound La 0.51 Li 0.34 Ti 2.94 、Li 3.4 V 0.4 Ge 0.6 O4, Li2O-Nb2O5, LiAlGaSPO4; - Formulations based on: Li2CO3, B2O3, Li2O, Al(PO3)3LiF, P2S3, Li2S, Li3N, Li 14 Zn(GeO4)4、Li 3.6 Ge 0.6 V 0.4 O4、LiTi2(PO4)3、Li 3.25 Ge 0.25 P 0.25 S4, Li 1.3 Al 0.3 Ti 1.7 (PO4)3、Li 1+x Al x M 2-x (PO4)3, where M = Ge, Ti and / or Hf and where 0 < x < 1, Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 , where 0 ≤ x ≤ 1 and 0 ≤ y ≤ 1.

11. The method according to claim 10, characterized in that The material P is an inorganic material selected from the group consisting of: - Garnet, selected from: Li7La3Zr2O 12 ;Li6La2BaTa2O 12 ;Li 5.5 La3Nb 1.75 In 0.25 O 12 ;Li5La3M2O 12 , where M = Nb or Ta or a mixture of these two compounds; Li 7-x Ba x La 3-x M2O 12 , where 0 ≤ x ≤ 1 and M = Nb or Ta or a mixture of these two compounds; Li 7-x La3Zr 2-x M x O 12 , where 0 ≤ x ≤ 2 and M = Al, Ga or Ta or a mixture of two or three of these compounds; - lithiated phosphates selected from the following types of lithiated phosphates: NaSICON, Li3PO4; LiPO3; Li3Al 0.4 Sc 1.6 (PO4)3, called "LASP"; Li 1.2 Zr 1.9 Ca 0.1 (PO4)3;LiZr2(PO4)3;Li 1+3x Zr2(P 1-x Si x O4)3, of which 1.8 <x < 2.3;Li 1+6x Zr2(P 1-x B x O4)3, where 0 ≤ x ≤ 0.25; Li3(Sc 2-x M x )(PO4)3, where M=Al or Y and 0≤ x ≤ 1; Li 1+x M x (Sc) 2-x (PO4)3, where M = Al, Y, Ga or a mixture of these three compounds and 0 ≤ x ≤ 0.8; Li 1+x M x (Ga 1-y Sc y ) 2-x (PO4)3, where 0 ≤ x ≤ 0.8; 0 ≤ y ≤ 1 and M = Al or Y or a mixture of these two compounds; Li 1+x M x (Ga) 2-x (PO4)3, where M = Al, Y, or a mixture of these two compounds and 0 ≤ x ≤ 0.8; Li 1+x Al x Ti 2-x (PO4)3, where 0 ≤ x ≤ 1, is called "LATP"; or Li 1+x Al x Ge 2-x (PO4)3, where 0 ≤ x ≤ 1, is called "LAGP"; or Li 1+x+z M x (Ge 1-y Ti y ) 2-x Si z P 3-z O 12 , wherein 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-y O 12 , where 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-y O 12 , where M = Al, Y, Ga or a mixture of these three compounds and Q = Si and / or Se, 0 ≤ x ≤ 0.8 and 0 ≤ y ≤ 1; or Li 1+x+y+z M x (Ga 1-y Sc y ) 2-x Q z P 3-z O 12 , where 0 ≤ x ≤ 0.8, 0 ≤ y ≤ 1.0 ≤ z ≤ 0.6, where M = Al or Y or a mixture of these two compounds and Q = Si and / or Se; or Li 1+ x Zr 2-x B x (PO4)3, where 0 ≤ x ≤ 0.25; or Li 1+x Zr 2-x Ca x (PO4)3, where 0 ≤ x ≤ 0.25; or Li 1+ x M 3 x M 2-x P3O 12 , where 0 ≤ x ≤ 1 and M 3 = Cr, V, Ca, B, Mg, Bi and / or Mo, M = Sc, Sn, Zr, Hf, Se or Si, or a mixture of these compounds; Li 1+2x Ca x Zr 2-x (PO4)3, where 0 ≤ x ≤ 0.25; - Lithiated borate selected from: Li3(Sc 2-x M x )(BO3)3, where M=Al or Y and 0 ≤ x ≤ 1; Li 1+x M x (Sc) 2-x (BO3)3, where M = Al, Y, Ga or a mixture of these three compounds and 0 ≤ x ≤ 0.8; Li 1+x M x (Ga 1-y Sc y ) 2-x (BO3)3, where 0 ≤ x ≤ 0.8, 0 ≤ y ≤ 1 and M = Al or Y; Li 1+x M x (Ga) 2-x (BO3)3, where M = Al, Y, or a mixture of these two compounds and 0 ≤ x ≤ 0.8; Li3BO3, Li3BO3-Li2SO4, Li3BO3-Li2SiO4, Li3BO3-Li2SiO4-Li2SO4; - Oxynitride, selected from Li3PO 4-x N 2x / 3 、Li4SiO 4-x N 2x / 3 、Li4GeO 4-x N 2x / 3 , where 0 < x < 4 or Li3BO 3- x N 2x / 3 , where 0 < x < 3; - Lithiated oxides, selected from Li7La3Zr2O 12 or Li 5+x La3(Zr x ,A 2-x )O 12 , where A = Sc, Y, Al, Ga and 1.4≤ x ≤ 2 or Li 0.35 La 0.55 TiO3 or Li 3x La 2 / 3-x TiO3, where 0 ≤ x ≤ 0.16; and - Silicates selected from the group consisting of Li2Si2O5, Li2SiO3, Li2Si2O6, LiAlSiO4, Li4SiO4, LiAlSi2O6.

12. The method according to claim 10, characterized in that Lithiated forms of chalcogenides include: Li x V2O5, where 0 < x ≤ 2, Li x V3O8, where 0 < x ≤ 1.7, Li x TiS2, where 0 < x ≤ 1, lithium titanium oxysulfide Li x TiO y S z , where z = 2-y, 0.3 ≤ y ≤ 1, Li x WO y S z , Li x CuS, Li x CuS2; Mixed silicon tin oxynitrides include SiSn 0.87 O 1.2 N 1.72 ; The carbon is selected from graphene and carbon nanotubes; For formula Li d A 1 x A 2 y (TO4) z Garnet, d is 3 to 9, x is 2.8 to 3.2, and y is 1.9 to 2.1; Li x PO y N z including Li 2.9 PO 3.3 N 0.46 。 13. The method according to claim 12, characterized in that For formula Li d A 1 x A 2 y (TO4) z For garnet, d is 4 to 8.

14. The method according to claim 1 or 2, characterized in that The nanoparticles of material P include nanoparticles consisting of a core of material P and a shell.

15. The method according to claim 14, characterized in that The shell is formed from a material that is an electron conductor.

16. The method according to claim 14, characterized in that The shell is formed of a material that is an electronic insulator and a cation conductor.

17. The method according to claim 14, characterized in that The shell is formed from a material that is an electronic insulator and a lithium ion conductor.

18. A method for manufacturing a lithium-ion battery, comprising the steps of the method for manufacturing a dense layer according to any one of claims 1 to 17. The method according to claim 18 , wherein a porous layer for forming a separator is also deposited.

20. The method of claim 19, wherein the porous layer is a mesoporous layer having a mesopore volume between 25% and 75%.

21. The method of claim 20, wherein the mesopore volume is between 30% and 60%.

22. The method according to any one of claims 19 to 21, wherein the method for depositing the porous layer is a method selected from the group consisting of electrophoresis, printing, and coating, deposited using a suspension of nanoparticle aggregates or agglomerates.

23. The method according to claim 22, wherein the printing method is selected from inkjet printing and flexographic printing, and the coating method is selected from roll coating, curtain coating, knife coating, slot coating, and dip coating.

24. The method according to any one of claims 19 to 21, wherein a material having an average primary diameter D of at least one inorganic material is used. 50 A colloidal suspension of nanoparticle aggregates or agglomerates between 2 nm and 100 nm, typically with an average diameter D 50 Between 50 nm and 300 nm.

25. The method according to any one of claims 19 to 21, wherein a material having an average primary diameter D of at least one inorganic material is used. 50 A colloidal suspension of nanoparticle aggregates or agglomerates between 2 nm and 60 nm, typically with an average diameter D 50 Between 100 nm and 200 nm.

26. The method according to claim 22, wherein the layer thus obtained is dried and consolidated by compression and / or heating to obtain a porous layer.

27. The method of claim 26, wherein the porous layer is a mesoporous inorganic layer.

28. The method of any one of claims 19 to 21, wherein the porous layer is deposited on the dense layer.

29. The method of any one of claims 19 to 21, wherein the dense layer is deposited on the porous layer.

30. The method according to any one of claims 19 to 21, wherein the porous separator is impregnated with a mobile lithium ion carrier liquid selected from the group consisting of: an electrolyte composed of at least one aprotic solvent and at least one lithium salt; an electrolyte composed of at least one ionic liquid or ionic multi-liquid and at least one lithium salt; a mixture of at least one aprotic solvent and at least one ionic liquid or ionic multiliquid and at least one lithium salt; rendering the polymer an ion conductor by incorporating at least one lithium salt; and By adding liquid electrolytes into the polymer phase or mesoporous structure, the polymer can be made into an ion conductor. The polymer is selected from poly(ethylene oxide), poly(propylene oxide), polydimethylsiloxane, polyacrylonitrile, poly(methyl methacrylate), poly(vinyl chloride), poly(vinylidene fluoride), PVDF-hexafluoropropylene.

31. A dense layer, which can be prepared according to the method according to any one of claims 1 to 17.

32. The dense layer according to claim 31, characterized in that It is selected from the anode, cathode or electrolyte of an electrochemical device.

33. The dense layer according to claim 32, characterized in that The electrochemical device is a lithium-ion battery.

34. An electrochemical device comprising at least one dense layer according to any one of claims 31 to 33.

35. The electrochemical device according to claim 34, characterized in that It consists of a battery with a capacity not exceeding 1 mA h.

36. The electrochemical device according to claim 35, characterized in that The battery is a lithium-ion battery.

37. The electrochemical device according to claim 36, characterized in that A lithium-ion battery comprises an anode and / or a cathode which is the dense layer according to any one of claims 31 to 33.

38. The electrochemical device according to claim 37, characterized in that Lithium-ion batteries include a liquid electrolyte impregnated into a porous separator that separates the anode and cathode.

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