Method for manufacturing assembly consisting of a separator and a porous electrode, assembly consisting of a separator and a porous electrode, and electrochemical device comprising the assembly

Abstract

The present invention relates to a method for manufacturing an electrochemical device selected from the group consisting of lithium-ion batteries with a capacity greater than 1 mAh, capacitors, supercapacitors, resistors, inductors, transistors, photovoltaic cells, and fuel cells, implementing a method for manufacturing an assembly consisting of a porous electrode and a porous separator, wherein the electrode comprises a porous layer deposited on a substrate, the porosity being between 20% and 60% (by volume) and the average diameter of the pores being less than 50 nm.

Description

Technical Field

[0001] The present invention relates to the field of electrochemistry, and more particularly to electrochemical systems. More specifically, it relates to porous electrode / diaphragm assemblies that can be used in electrochemical devices such as high-power batteries (including lithium-ion batteries) with a capacity greater than 1 mAh, sodium-ion batteries, lithium-air batteries, fuel cells, and photovoltaic cells. The present invention is applicable to both negative and positive electrodes. These porous electrode / diaphragm assemblies can be impregnated with a solid electrolyte that does not contain a liquid phase or liquid electrolyte.

[0002] The present invention also relates to a method for preparing a porous electrode / separator assembly comprising nanoparticles of the electrode material and nanoparticles of the inorganic material that will constitute the separator, as well as the porous electrode / separator assembly obtained thereby. The present invention also relates to a method for manufacturing an electrochemical device comprising at least one of these components, as well as the device obtained thereby; these devices are preferably lithium-ion batteries. Background Art

[0003] An ideal battery for powering autonomous electrical devices (e.g., portable phones and computers, portable tools, autonomous sensors) or electric vehicle traction should have a long service life, be able to store large amounts of energy and power, and not risk overheating or even exploding.

[0004] Currently, these electronic devices are primarily powered by lithium-ion batteries, which offer the best energy density among the various proposed energy storage technologies. A variety of structures, electrode chemistries, and separator compositions are used to produce these batteries. Numerous articles and patents describe methods for manufacturing lithium-ion batteries; a detailed bibliography is provided in the publication "Advances in Lithium-Ion Batteries" (W. van Schalkwijk and B. Scrosati, Kluever Academic / Plenum Publishers, 2002).

[0005] Electrodes for lithium-ion batteries can be manufactured using coating techniques (particularly roll coating, blade coating, tape casting, and slot die coating). In these methods, an ink consisting of active material particles in powder form is deposited on a substrate surface; the average particle size of the particles constituting the powder is typically between 5 μm and 15 μm.

[0006] These techniques can produce layers with thicknesses ranging from about 50 μm to about 400 μm. The power and energy of the battery can be adjusted by adjusting the thickness and porosity of the battery layers and the size of the active particles that make up the battery layers.

[0007] The ink (or paste) deposited to form the electrode contains particles of active material, but also an (organic) binder, carbon powder to ensure electrical contact between the particles, and 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 50% to 70% of the deposited volume, which means that the porosity between the particles is typically around 30% to 50%.

[0008] In order to best optimize the volumetric energy density of lithium-ion batteries produced using conventional manufacturing methods, it is very useful to reduce the porosity of the electrodes; thus, the amount of active ingredient per unit volume of the electrode is increased. This can be done in a variety of ways.

[0009] In extremely dense layers, layers without pores can be used; therefore, the volumetric energy density of the electrode is maximized. Such dense layers can be produced using vacuum deposition techniques such as physical vapor deposition (PVD). However, because these layers without pores (called "all-solid-state layers") cannot contain liquid electrolytes to facilitate ion transport or electronically conductive fillers to facilitate charge transport, their thickness in the battery must be kept to within a few micrometers, otherwise the resistance would be too high. These deposition techniques can be used to manufacture microbatteries.

[0010] It is also possible to optimize conventional inking techniques, thereby increasing the density of the layers obtained after calendering. It has been shown that by optimizing the particle size distribution of the deposited particles, the density of the layer can reach 70% (see J. Ma and LCLim, "Effect of particle size distribution of sintering of agglomerate-free submicron alumina powder compacts", published in J. Europ. Ceramic Soc. 22 (13), p. 2197-2208 in 2002). It is estimated that the volume energy density of an electrode with a porosity of 30% containing a conductive filler and impregnated with a lithium ion conductive electrolyte is higher, by about 35%, than that of the same electrode with a porosity of 50% composed of monodisperse particles. In addition, the thickness of these electrodes can be greatly increased due to the impregnation of a highly ionically conductive phase and the addition of an electronic conductor, compared to vacuum deposition techniques that produce dense but more resistive layers. The increase in electrode thickness increases the energy density of the battery cell obtained therefrom.

[0011] However, while this allows for increased energy density in electrodes, such a size distribution of active material particles is not without its problems. Particles of different sizes in an electrode have different capacitances. Under the same charge and / or discharge current, they will locally charge and / or discharge more or less rapidly, depending on their size. When the battery is no longer subjected to the current, the local charge states between the particles will balance again, but during transient phases, local imbalances can cause particles to be locally stressed, pushing them outside their stable voltage range. These local charge imbalances become more pronounced as current density increases significantly. Consequently, these imbalances can lead to losses in battery cycling performance, safety risks, and power limitations. This is also true when the electrode’s porosity—that is, when the particle size distribution—is non-uniform; this non-uniformity makes it more difficult to wet the electrode pores.

[0012] In the open paper “A study on the Effect of Porosity and Particle Size Distribution On Li-Ion Battery Performance” published by ST Taleghani et al. in the journal J. Electrochem. Soc. 164(11), p. E3179-E3189 in 2017, the effect of the particle size distribution of active material particles on the electrode current / voltage relationship was studied through numerical simulation.

[0013] According to existing technologies, the size of active material particles used with the above-mentioned electrode inking technology is generally between 5μm and 15μm. The contact between each particle is essentially point contact, and the particles are bound together with an organic binder, which in most cases is polyvinylidene fluoride (PVDF).

[0014] All-ceramic mesoporous electrode layers for lithium-ion batteries can be deposited by electrophoresis; this deposition method is known from WO 2019 / 215 407 (I-TEN). They can be impregnated with liquid electrolytes, but their resistivity remains high.

[0015] The liquid electrolytes used to impregnate the porous electrodes consist of aprotic solvents in which lithium salts are dissolved. They are highly flammable and can cause violent combustion in batteries, especially when the active cathode material encounters a voltage range beyond its stable voltage range or when localized hot spots develop within the battery.

[0016] In order to solve these safety issues inherent in the structure of lithium-ion batteries, we can start from three aspects.

[0017] According to the first aspect, organic solvent-based electrolytes can be replaced with temperature-stable ionic liquids. However, ionic liquids do not wet the surfaces of organic materials, and the presence of PVDF and other organic binders in conventional lithium-ion battery electrodes prevents the anchor electrode from being wetted by such electrolytes, thus impacting electrode performance. Ceramic separators have been developed to address this issue at the electrolyte junction between electrodes, but the presence of organic binders in the electrodes still poses a challenge to the use of ionic liquid electrolytes.

[0018] According to the second aspect, one can seek to homogenize the particle size to avoid local imbalances in the state of charge, which during intense discharge could cause local stress on the active material, exceeding its operating voltage range. This optimization would come at the expense of the battery's energy density.

[0019] According to a third aspect, the distribution and distribution of the conductive filler (typically carbon black) can be homogenized in the electrode, avoiding localized areas of greater resistance that can form hot spots during battery-powered operation.

[0020] More specifically, the cost of manufacturing battery electrodes according to existing methods depends in part on the properties of the solvents and inks used. Besides the inherent cost of the active materials, the manufacturing cost of the electrodes primarily comes from the complexity of the inks used (binder, solvent, carbon black). The primary solvent used in lithium-ion battery electrode production is N-methyl-2-pyrrolidone (NMP). NMP is an excellent solvent for PVDF, which acts as a binder in the ink formulation.

[0021] Drying NMP in electrodes is a real economic issue. NMP has a high boiling point and very low vapor pressure, making it difficult to dry in an industrial environment. The solvent vapors must be collected and reprocessed. Furthermore, to ensure good electrode adhesion to the substrate, the NMP drying temperature must be kept low, which further increases drying time and costs. This is described in the article "Technical and economic analysis of solvent-based lithium-ion electrode drying with water and NMP" published by DL Wood et al. in the journal Drying Technology, vol. 36, no. 2 (2018).

[0022] Other, cheaper solvents (particularly water and ethanol) can be used to produce inks. However, their surface tension is greater than that of NMP, resulting in poorer wettability of the metal current collector surface. Furthermore, particles tend to agglomerate in water, particularly carbon black nanoparticles. This agglomeration leads to uneven distribution of the components (binder, carbon black, etc.) that go into the electrode composition. Furthermore, whether using water or ethanol, trace amounts of water can adsorb on the surface of the active material particles, even after drying.

[0023] Finally, to obtain a low-cost and efficient electrode, in addition to the problems related to ink formulation, it must be remembered that the ratio of energy density to power density of the electrode can be adjusted by the particle size of the active material and indirectly by the porosity and thickness of the electrode layer. The article by J. Newman ("Optimization of Porosity and Thickness of a Battery Electrode by Means of a Reaction-Zone Model", J. Electrochem. Soc., 142 (1), p. 97-101 (1995)) shows the influence of the thickness of the electrode and its porosity on its discharge rate (power) and energy density.

[0024] Furthermore, when batteries are manufactured, it is known that a separator is placed between the electrodes. The electrodes and separator of each basic battery are usually impregnated with a liquid electrolyte. The separators used in lithium-ion batteries are usually polymer membranes whose pores are impregnated with a liquid electrolyte containing a lithium salt (such as LiPF6). The polymer form of these separators creates wettability issues with ionic liquids. These separators can be surface treated or mineral fillers can be integrated into them to improve their mechanical strength and wettability with ionic liquids.

[0025] For mechanical strength, these separators are typically 25 microns thick. They must be able to withstand the electrical currents applied during the battery manufacturing steps. To this end, they typically consist of several polymer layers. These are primarily polyethylene (PE) and polypropylene (PP), which provide safety functions, particularly sealing pores in the event of local overheating, and mechanical functions, respectively.

[0026] These separators have micropores that can be impregnated with electrolyte, thus ensuring ion mobility. During battery use, lithium dendrites can form within the thickness of the separator, creating the risk of thermal runaway. Conductive carbon black nanoparticles can also break off from the electrodes and enter the separator, creating the risk of internal short circuits. Defects in the separator can exacerbate these risks.

[0027] Furthermore, a thicker separator reduces the energy and power density of a battery containing it. The thicker the separator, the greater the ionic resistance between the anode and cathode. Furthermore, the volume occupied by the separator does not store energy; the thinner the separator, the better the specific energy density of the battery unit.

[0028] To reduce these safety risks and the resulting reduction in battery performance, solid electrolytes, usually in the form of polymers, have been developed. These solid electrolytes are deposited directly on the electrodes, allowing their thickness to be reduced; thus, the problem of maintaining their rigidity during battery manufacturing no longer arises.

[0029] However, the risk of dendrite formation in solid electrolytes has not been fully addressed. In fact, dendrites can form in solid electrolytes even in the absence of a liquid electrolyte. This formation is more likely due to the poor electrical insulation of the solid electrolyte and the lithium-phobic nature of the electrolyte material.

[0030] When the solid electrolyte is in the form of a polymer, the absence of a dissolved liquid electrolyte (either dissolved at room temperature or in the form of an ionic liquid) in the polymer can limit or even prevent the appearance of dendrites.

[0031] The risk of lithium dendrites primarily exists when the anode is operated at low potentials. Titanate-based anodes, when operated at 1.5V, do not present the risk of lithium dendrite formation during battery charging. These anodes are also particularly well-suited for applications requiring fast charging.

[0032] To overcome these various problems, solid, ceramic, mesoporous electrolyte layers have been developed whose pores can be impregnated with liquid electrolytes (e.g., ionic liquids); this is known from WO 2019 / 215 411 (I-TEN). These electrolytes are particularly suitable for use with anodes operating at relatively high insertion potentials, as there is no risk of lithium dendrite formation. Furthermore, the ceramic nanoparticles used in these electrolytes are stable over a wide potential range and are particularly hard. Therefore, they can be deposited thinly on lithium-ion battery electrodes, resulting in extremely high energy and power densities.

[0033] During the manufacturing process, these solid, ceramic, mesoporous electrolyte layers are sintered in air. The heat treatment used allows the calcination of any organic residues they contain (solvents and / or stabilizers and / or binders used in the nanoparticle suspension) while preventing these from being converted into a thin carbon layer that could impair electrical insulation, particularly by short-circuiting electrodes of opposite polarity. After this heat treatment, the resulting inorganic separator can be easily impregnated with a liquid electrolyte (solvated and / or ionic liquids at room temperature). It is particularly suitable for ceramic electrodes that can withstand heat treatment.

[0034] On the other hand, in order to produce batteries with very high energy densities, it is recommended to use negative electrodes with the lowest possible lithium insertion potential. To prevent the formation of dendrites in such high-energy batteries, other electrolytes have been developed and are described in the application WO 2019 / 215410 (I-TEN). These electrolytes have a homogeneous composite structure, including a solid electrolyte / PEO volume ratio greater than 35%. This structure allows the production of solid electrolytes that do not form lithium dendrites with good ionic conductivity, and the PEO does not contain lithium salts.

[0035] The problem to be solved by the present invention is to provide a porous electrode / diaphragm assembly for a lithium-ion battery, wherein the lithium-ion battery is equipped with electrodes with very high energy density and power density, and a diaphragm with a stable mechanical structure and good thermal stability, which can operate reliably and has a good cycle life and higher safety.

[0036] Another problem to be solved by the present invention is to provide a method for manufacturing the porous electrode / diaphragm assembly, which is simple, safe, fast, easy to implement, easy to industrialize and low in cost.

[0037] Another object of the present invention is to provide a method for manufacturing a battery comprising the porous electrode / separator assembly of the present invention.

[0038] Another object of the present invention is to provide a rigid structure battery with long life, high power density, improved reliability and mechanical resistance to shock and vibration. Summary of the Invention

[0039] The present invention is applicable to an assembly consisting of a porous electrode and a porous membrane. The membrane can serve as a main structure for accommodating an ion-conducting electrolyte; the ion-conducting electrolyte can also penetrate the porous electrode.

[0040] To overcome the inherent safety issues of traditional lithium-ion battery structures, the inventors followed three principles:

[0041] According to the first principle, organic solvent-based electrolytes should be replaced with mixtures of organic solvents and ionic liquids, or ionic liquids, which have extremely high temperature stability. However, ionic liquids do not wet the surfaces of organic materials, and the presence of PVDF and other organic binders in conventional battery electrodes prevents the electrodes from being wetted by such electrolytes, thus affecting electrode performance. Ceramic separators have been developed to address this issue at the electrolyte junction between electrodes, but the presence of organic binders in the electrodes still poses a problem for the use of ionic liquid electrolytes.

[0042] According to the second criterion, one can seek to homogenize the particle size to avoid local imbalances in the state of charge, which, during intense discharge, could cause local stresses in the active material beyond its conventional operating voltage range.

[0043] According to the third criterion, the distribution and distribution of the conductive additive (“conductive filler”; in practice only carbon black is used) can be homogenized in the electrode, avoiding localized areas of greater resistance that could form hot spots during battery-powered operation.

[0044] According to the invention, this problem is solved by an assembly consisting of a porous electrode and a separator for a lithium-ion battery, said assembly being completely porous, preferably mesoporous, free of organic binders, having a porosity between 25% and 50%, and having channels and pores of uniform size within the assembly, so as to ensure a perfect dynamic balance of the battery.

[0045] The porosity (expressed as relative pore volume) of the electrodes and the separator may be the same or different; preferably, they are different. This can be achieved by a two-step thermal consolidation, one for the electrodes deposited before the separator and one for the electrode-separator assembly. The porosity of the electrodes is preferably between 25% and 35% to optimize energy density, and the porosity of the separator is preferably between 40% and 60% (preferably between 45% and 55%) to optimize ionic conduction. In a particularly advantageous embodiment of the invention, the porosity of the electrodes is approximately 30% and the porosity of the separator is approximately 50%. Below 25%, impregnation becomes difficult and incomplete because the pores can at least partially close.

[0046] By depositing agglomerates and / or aggregates of nanoparticles of the active electrode material P and the corresponding inorganic material E forming the separator on a substrate, a completely solid, organic-free porous structure, preferably a mesoporous structure, of the porous electrode and the corresponding separator is obtained. The size of the primary particles constituting these agglomerates and / or aggregates is in the nanometer or tens of nanometer range, and the agglomerates and / or aggregates contain at least four primary particles.

[0047] In a first embodiment, the substrate may be a substrate capable of acting as a current collector, or in a second embodiment, an intermediate temporary substrate, as will be explained in more detail below.

[0048] Using agglomerates with diameters of tens or even hundreds of nanometers, rather than unaggregated primary particles, each with a size in the nanometer or tens of nanometer range, can increase deposition thickness. Agglomerates must be less than 300 nm in size. Sintering agglomerates larger than 500 nm will not produce a mesoporous continuous film. In this case, two different porosities are observed in the deposition: the porosity between agglomerates and the porosity within the agglomerates.

[0049] In fact, it has been observed that during the drying of nanoparticle deposits on substrates capable of acting as current collectors, cracks appear in the layer. It can be seen that the appearance of these cracks depends essentially on the size of the particles, the compactness of the deposit, and their thickness. The limiting thickness of the cracks is determined by the following relationship:

[0050]

[0051] where h max is the critical thickness, G is the nanoparticle shear modulus, M is the coordination number, is the volume fraction of nanoparticles, R is the particle radius, and γ is the interfacial tension between solvent and air.

[0052] Therefore, the use of mesoporous agglomerates composed of primary nanoparticles having a size at least 10 times smaller than that of the agglomerates can significantly increase the limit thickness of layer cracks. Similarly, a small amount of solvent with lower surface tension (such as isopropyl alcohol (IPA)) can be added to water or ethanol to improve the wettability and adhesion of the deposition and reduce the risk of cracking. In order to increase the deposition thickness and limit or eliminate the occurrence of cracks, adhesives and dispersants can be added. These additives and organic solvents can be removed by heat treatment (such as degreasing) under air conditions during the heat treatment performed during the sintering process or before the sintering process.

[0053] In addition, for primary particles of the same size, the size of the agglomerates can be changed during the synthesis process by precipitation by adjusting the amount of ligand (e.g. polyvinyl pyrrolidone, PVP for short) in the synthesis reactor. As a result, inks containing agglomerates with very dispersed sizes or with two complementary size populations can be produced, thereby maximizing the density of the agglomerate deposition. Unlike the sintering of non-agglomerated nanoparticles, the sintering conditions between agglomerates of different sizes do not change. These are the primary nanoparticles that constitute the agglomerates that will be bonded together. Regardless of the size of the agglomerates, these primary nanoparticles have the same size. The size distribution of the agglomerates will increase the density of the deposited layer and increase the contact points between the nanoparticles, but will not change the consolidation temperature.

[0054] After partial sintering, a porous (preferably mesoporous) layer or plate is obtained, free of carbon black or organic compounds, in which all the nanoparticles are bound together (by the necking phenomenon, which is also known).

[0055] As described above, the method for preparing the mesoporous deposition is used to prepare the porous electrode and the separator of the assembly consisting of the porous electrode and the separator according to the present invention.

[0056] The porous (preferably mesoporous) layer thus obtained is fully solid and ceramic. During cycling, there is no longer a risk of loss of electrical contact between the active material particles, which may improve the battery's cycling performance. Furthermore, after sintering, the electrode adheres perfectly to the metal substrate on which it was deposited or transferred (when initially deposited on an intermediate substrate).

[0057] The heat treatment performed at high temperature sintered the nanoparticles together, completely dried the electrode, and removed any traces of water or solvent or other organic additives (stabilizers, binders) adsorbed on the surface of the active material particles. The high temperature heat treatment (sintering) can be preceded by a low temperature heat treatment (degreasing) to dry the deposited or deposited electrode and remove traces of water or solvent or other organic additives (stabilizers, binders) adsorbed on the surface of the active material particles; this degreasing can be performed in an oxidizing atmosphere.

[0058] The porosity of the final electrode can be adjusted by sintering time and temperature, which can be adjusted within a porosity range of 50% to 25%, depending on the energy density requirements.

[0059] In all cases, the power density of the obtained electrodes remained very high due to the mesoporosity. Moreover, regardless of the size of the mesopores in the active material (it is understood that the concept of nanoparticles no longer applies to three-dimensional structured materials with channels and mesopore networks after sintering), the dynamic cell balance remained perfect, which helped to maximize the power density and extend the battery life.

[0060] The electrodes of the assembly described herein have a high surface area, which reduces their ionic resistance. However, to deliver maximum power to the electrodes, they must also maintain good electronic conductivity to avoid resistive losses in the battery. The greater the thickness of the electrode, the more important it is to improve the battery's electronic conductivity. Furthermore, electronic conductivity must be completely uniform across the entire electrode to avoid the formation of localized hot spots.

[0061] According to the present invention, a coating of conductive material is deposited on and within the pores of the porous layer of active material. This conductive material can be deposited by atomic layer deposition (ALD) or from a liquid precursor. The conductive material can be carbon. This conductive material is deposited only on the electrodes, not on the separator.

[0062] To deposit the carbon layer from a liquid precursor, the mesoporous layer can be immersed in a solution rich in carbon precursor (e.g., a sucrose solution). The electrode is then dried and heat-treated under nitrogen at a temperature sufficient to pyrolyze the carbon precursor. This results in a very thin, perfectly distributed carbon coating over the entire inner surface of the electrode. This coating provides good electronic conduction to the electrode, regardless of its thickness. It should be noted that this treatment can be performed after sintering, because the electrode is completely solid, free of organic residues, and able to withstand the thermal cycles imposed by various heat treatments.

[0063] Then, according to the method for producing mesoporous deposition on the porous electrode of the component as described above, the separator of the component of the present invention is obtained.

[0064] The separator thus obtained is a fully solid ceramic separator with good mechanical strength. Moreover, after sintering, the inorganic layer deposited adheres perfectly to the porous electrode, thus forming the assembly according to the present invention.

[0065] Heat treatment at high temperatures sintered the nanoparticles together, completely dried the separator, and removed any traces of water adsorbed on the surface of the inorganic E particles that make up the separator. Depending on the sintering time and temperature, the porosity of the separator can be adjusted.

[0066] The assembly of the porous electrode and the separator according to the present invention can advantageously be assembled onto the electrode according to the present invention or onto another assembly, thereby obtaining a functional battery.

[0067] A first object of the present invention is a method for manufacturing an assembly consisting of a porous electrode and a porous separator, in particular for an electrochemical device selected from the group consisting of: lithium-ion batteries with a capacity greater than 1 mAh; sodium-ion batteries; lithium-air batteries; photovoltaic cells; fuel cells,

[0068] The electrode comprises a porous layer deposited on a substrate, said layer being binder-free, having a porosity between 20% and 60% (by volume), preferably between 25% and 50%, the average diameter of the pores being less than 50 nm,

[0069] The separator comprises a porous inorganic layer deposited on the electrode, the porous inorganic layer being free of binder, having a porosity between 25% and 60% (by volume), preferably between 30% and 50%, and an average pore diameter of less than 50 nm,

[0070] The manufacturing method is characterized in that:

[0071] (a) providing a substrate, a first colloidal suspension comprising monodisperse primary nanoparticle aggregates or agglomerates of at least one active electrode material P, wherein the average primary diameter D of the primary nanoparticles is 50The average diameter D of the aggregates or agglomerates is between about 2 nm and 150 nm, preferably between about 2 nm and about 100 nm, preferably between 2 nm and about 60 nm, even more preferably between 2 nm and 50 nm. 50 is between about 50 nm and about 300 nm (preferably between about 100 nm and about 200 nm), and a second colloidal suspension comprising aggregates or agglomerates of nanoparticles of at least one inorganic material E, said nanoparticles having an average primary diameter D 50 The average diameter D of the aggregates or agglomerates is between about 2 nm and about 100 nm, preferably between about 2 nm and about 60 nm. 50 is between about 50 nm and about 300 nm (preferably between about 100 nm and about 200 nm);

[0072] (b) depositing a layer of the colloidal suspension or paste provided in step (a) on at least one surface of the substrate by a technique preferably selected from the group consisting of electrophoresis, printing, in particular inkjet printing and flexographic printing, and coating, in particular knife coating, roll coating, curtain coating, dip coating and extrusion slot coating;

[0073] (c) if appropriate, before or after separation of the layer obtained in step (b) from its intermediate substrate, drying the layer, then optionally subjecting the dried layer to a heat treatment, preferably under an oxidizing atmosphere, and consolidating it by compression and / or heating to obtain a porous (preferably inorganic mesoporous) layer;

[0074] (d) depositing a coating of a conductive material on and within the pores of the porous layer to form the porous electrode;

[0075] (e) depositing a porous inorganic layer on the porous electrode obtained in step (d) using the second colloidal suspension provided in step (a) by a technique preferably selected from the group consisting of: electrophoresis, printing, in particular inkjet printing and flexographic printing, and coating, in particular doctor blade coating, roll coating, curtain coating, dip coating and extrusion slot coating;

[0076] (f) drying the porous inorganic layer of the structure obtained in step (e), preferably under air flow, and heat-treating it in air at a temperature below 500° C., preferably at about 400° C., to obtain the assembly consisting of a porous electrode and a porous separator,

[0077] It should be understood that the substrate may be a substrate or an intermediate substrate capable of acting as a current collector. Advantageously, after the heat treatment of step (f), the assembly consisting of the porous electrode and the separator is impregnated with an electrolyte, preferably a phase containing lithium ions, the electrolyte being selected from the group consisting of:

[0078] o an electrolyte consisting of at least one aprotic solvent and at least one lithium salt;

[0079] o an electrolyte composed of at least one ionic liquid or poly(ionic liquid) and at least one lithium salt;

[0080] o Mixtures of aprotic solvents and ionic liquids or poly(ionic liquids) and lithium salts;

[0081] o ion-conducting polymers produced by the addition of at least one lithium salt; and

[0082] o Ion-conducting polymers made by incorporating liquid electrolytes into the polymer phase or mesoporous structure.

[0083] Advantageously, after step d), the electrode obtained can be coated with an ion-conducting layer to improve the battery life and performance. The ion-conducting layer can be Li 1.3 Al 0.3 Ti 1.7 (PO4)3, nafion (perfluorosulfonic acid type polymer solution), Li3BO3, PEO, or a mixture of PEO and a phase carrying lithium ions (such as lithium salt).

[0084] In step (b), deposition may be performed on one side or both sides of the substrate.

[0085] Advantageously, when the substrate is an intermediate substrate, the layer is separated from the intermediate substrate in step (c) to form a porous plate after consolidation. The separation step can be performed before or after drying the layer obtained in step b).

[0086] Advantageously, when the substrate is an intermediate substrate, after step c) and before step d), a conductive plate is provided, covered on at least one side, preferably on both sides, with a thin layer of conductive glue or a thin layer of nanoparticles of at least one active electrode material P, and then at least one porous plate is bonded to one side, preferably on each side, of the conductive plate, thereby obtaining a porous (preferably mesoporous) layer on the substrate that can serve as a current collector.

[0087] Advantageously, when the colloidal suspension or paste provided in step (a) contains organic additives, such as ligands, stabilizers, binders or residual organic solvents, the layer dried in step c) and / or the porous inorganic layer dried in step f) is preferably subjected to a heat treatment under an oxidizing atmosphere. When the heat treatment is carried out under an oxidizing atmosphere or before the step of consolidating the dried layer in step c), this heat treatment allowing degreasing can be carried out simultaneously with consolidation (sintering).

[0088] In a first embodiment, the substrate is a substrate capable of acting as a current collector. The substrate on which the layer is deposited ensures the function of the current collector in the electrode. Its chemical properties must be compatible with the heat treatment (degreasing and / or sintering heat treatment) temperatures of step (c) of the porous electrode manufacturing method; in particular, it must not melt or form an oxide layer with excessive electrical resistance, nor react with the electrode material. Advantageously, a metal substrate is selected, which can be made, in particular, of tungsten, molybdenum, chromium, titanium, tantalum, stainless steel, or alloys of two or more of these materials. Such metal substrates are relatively expensive and can significantly increase the cost of the battery. Before depositing the layer of material P, the metal substrate can also be coated with a conductive or semiconducting oxide, which is particularly useful for protecting less expensive substrates such as copper and nickel. After step (c), the thickness of the layer is advantageously between approximately 1 μm and approximately 300 μm, preferably between approximately 1 μm and 150 μm, and more preferably between 10 μm and 50 μm or between 10 μm and 30 μm. When the substrate used is one capable of acting as a current collector, the thickness of the layer after step (c) is limited in order to avoid any cracking problems.

[0089] In a second embodiment, the substrate is an intermediate temporary substrate, such as a flexible substrate, which may be a polymer film. In this second embodiment, the deposition step is advantageously carried out on one side of the intermediate substrate in order to facilitate the subsequent separation of the layer from its substrate. In this second embodiment, the layer can be separated from its substrate after drying, preferably before heating, but at the latest at the end of step (c). After step (c), the thickness of the layer is advantageously less than or equal to 5 mm, advantageously between about 1 μm and about 500 μm. The thickness of the layer after step (c) is advantageously less than 300 μm, preferably between about 5 μm and about 300 μm, preferably between 5 μm and 150 μm.

[0090] Advantageously, the specific surface area of ​​the porous layer obtained at the end of step (c) is about 10 m 2 / g and about 500m 2 Its thickness is advantageously between 1 and 500 μm, preferably between approximately 4 and approximately 400 μm.

[0091] The thickness of the deposit obtained at the end of step (e) is advantageously between about 3 μm and about 20 μm and preferably between about 5 μm and about 10 μm.

[0092] Advantageously, the specific surface area of ​​the porous inorganic layer obtained at the end of step (f) is about 10 m 2 / g and about 500m 2 Its thickness is advantageously between 3 μm and 20 μm, preferably between 5 μm and 10 μm.

[0093] The particle size distribution of the primary particles of the active material P and / or the inorganic material E is preferably narrow. Preferably, the agglomerate preferably comprises at least three primary particles. The particle size distribution of the agglomerate is preferably polydisperse. In one embodiment, the particle size distribution of the agglomerate is bimodal, that is, it has two particle size distribution peaks, which are referred to as D1 and D2, where D1>D2; the ratio D2 / D1 can be, for example, between 3 and 7, preferably between 4 and 6; this avoids the formation of large voids and ensures good compactness of the mesoporous layer.

[0094] The nanoparticle suspension can be prepared in water or ethanol, or in a mixture of water and ethanol, or in a mixture of ethanol and isopropanol (with an isopropanol content of less than 3%). It does not contain carbon black.

[0095] For use with dip-coating or curtain-coating techniques, the suspension is advantageously characterized by a dry extract of at least 15%, preferably at least 50%.

[0096] The deposition of the conductive material coating can be performed by atomic layer deposition ALD technology or by immersing the layer in a liquid phase comprising a precursor of the conductive material and then converting the precursor into the conductive material.

[0097] Advantageously, the precursor is a carbon-rich compound, such as a carbohydrate, in particular a polysaccharide (e.g., sucrose, lactose, glucose). In this case, the conversion into the conductive material is performed by pyrolysis, preferably under an inert atmosphere (e.g., nitrogen). The conductive material may be carbon. Deposition can be performed, in particular, by ALD or immersion in a liquid phase containing a carbon precursor.

[0098] In the second embodiment, the method for manufacturing a porous electrode for a battery uses an intermediate polymer substrate (such as PET) and produces a strip called a "raw strip". The strip is then separated from its substrate; a plate or sheet (hereinafter referred to as a "plate", regardless of its thickness) is then formed. After cutting, the plates can be separated from their intermediate substrate. The plates are then calcined to remove organic components. The plates are then sintered to consolidate the nanoparticles until a mesoporous ceramic structure with a porosity between 25% and 50% is obtained. The thickness of the porous plate obtained in step (c) is advantageously less than or equal to 5 mm, preferably between about 1 μm and about 500 μm. The thickness of the layer after step (c) is advantageously less than 300 μm, preferably between about 5 μm and about 300 μm, preferably between 5 μm and 150 μm. A coating of conductive material is then deposited on and within the pores of the porous layer or porous plate, which, as just described, is preferably mesoporous;

[0099] In this second embodiment, a conductive plate is also provided. Both surfaces of the conductive plate are coated with a relatively thin intermediate layer of nanoparticles, preferably the same nanoparticle layer as the electrode plate, or both surfaces are coated with a thin layer of conductive adhesive. The thickness of the thin layer is preferably less than 1 μm. The plate can be a metal strip or a graphite plate.

[0100] The conductive plate is then inserted between the two plates of the previously obtained porous electrode and respectively between the two porous plates obtained after step c). The assembly is then hot-pressed so that the intermediate nanoparticle thin layer is transformed by sintering and the electrode / substrate / electrode assembly and the corresponding porous plate / substrate / porous plate assembly are consolidated respectively to obtain a rigid and complete subassembly. During the sintering process, the bond between the electrode layer, the corresponding porous plate and the intermediate layer is established by atomic diffusion; this phenomenon is called "diffusion bonding". The assembly is manufactured from two electrode plates of the same polarity, corresponding to two porous plates (usually between two anodes or between two cathodes), and a metal plate between the two electrode plates of the same polarity and the corresponding two porous plates to establish a parallel connection between them.

[0101] One of the advantages of the second embodiment is that it allows the use of inexpensive substrates, such as aluminum, copper or graphite strips. In fact, these strips cannot withstand the heat treatment of the consolidated deposited layer; gluing them to the electrode plates after the heat treatment also helps to prevent them from oxidizing.

[0102] According to another variant of the second embodiment, when the porous plate / substrate / porous plate assembly is obtained, then, as described above, a coating of conductive material can advantageously be deposited on and in the pores of the porous (preferably mesoporous) plates of the porous plate / substrate / porous plate assembly, in particular when the porous plates used are very thick.

[0103] The conductive material coating may be deposited by atomic layer deposition (ALD) or by immersing the porous layer in a liquid phase comprising a precursor of the conductive material and then converting the precursor into the conductive material.

[0104] As mentioned previously, this "diffusion-bonded" assembly can be performed individually, and the resulting electrode / substrate / electrode subassembly can be used to manufacture a battery. This diffusion-bonded assembly can also be achieved by stacking and hot-pressing the entire battery structure; in this case, a multilayer stack is assembled, including a first porous anode layer, its metal substrate, a second porous anode layer, a solid electrolyte layer, a first cathode layer, its metal substrate, a second cathode layer, a new solid electrolyte layer, and so on.

[0105] More specifically, the mesoporous ceramic electrode plates can be bonded to both sides of the metal substrate (which then finds the same configuration as deposited on both sides of the metal substrate).

[0106] Such an electrode / substrate / electrode subassembly can be obtained by bonding an electrode plate to a conductive plate capable of subsequently acting as current collector, or by depositing layers on a substrate capable of acting as current collector, in particular a metal substrate, and then sintering the layers.

[0107] Regardless of the specific embodiment of the electrode / substrate / electrode subassembly, the electrolyte membrane (separator) is then deposited on the latter.

[0108] Before depositing the electrolyte membrane (separator) on each electrode / substrate / electrode subassembly, necessary cuts can be made to produce a battery with multiple basic battery cells, and the subassemblies are then stacked (usually in a "head-to-tail" mode) and hot-pressed to join the electrodes together at the electrolyte membrane (separator).

[0109] Thermocompression bonding was performed at relatively low temperatures, likely due to the very small size of the nanoparticles. As a result, no oxidation of the substrate metal layer was observed.

[0110] In other embodiments of the assembly to be described below, a conductive glue (containing graphite) or a sol-gel type deposition containing conductive particles, or other metal strips, preferably low-melting-point metal strips (such as aluminum), are used; during thermomechanical (hot pressing) processing, the metal strips may be deformed by creep and achieve bonding between the plates.

[0111] If the electrode is used in a battery, it is preferred to choose an active material P that is dimensionally stable during the charge and discharge cycles. It can be chosen in particular from the group consisting of:

[0112] ○Oxide LiMn2O4; Li 1+x Mn 2-x O4, where 0 <x<0.15;LiCoO2;LiNiO2;LiMn1.5 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 elements, 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;

[0113] ○Li x M y O2, where 0.6 ≤ y ≤ 0.85; 0 ≤ x + y ≤ 2; M is selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn and Sb or a mixture of these elements; Li 1.20 Nb 0.20 Mn 0.60 O2;

[0114] ○Li 1+x Nb y Me z A p O2, where Me is at least one transition metal selected from: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs and Mt, where 0.6 < x < 1; 0 < y < 0.5; 0.25 ≤ z < 1; where A ≠ Me and A ≠ Nb, and 0 ≤ p ≤ 0.2;

[0115] ○Li x Nb y-a N a M z-b Pb O 2-c F c , where 1.2 < x ≤ 1.75; 0 ≤ y < 0.55; 0.1 < z < 1; 0 ≤ a < 0.5; 0 ≤ b < 1; 0 ≤ c < 0.8; where M, N, and P are at least one element selected from the following groups: Ti, Ta, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Zr, Y, Mo, Ru, Rh, and Sb;

[0116] ○Li 1.25 Nb 0.25 Mn 0.50 O2; Li 1.3 Nb 0.3 Mn 0.40 O2; Li 1.3 Nb 0.3 Fe 0.40 O2; Li 1.3 Nb 0.43 Ni 0.27 O2; Li 1.3 Nb 0.43 Co 0.27 O2; Li 1.4 Nb 0.2 Mn 0.53 O2;

[0117] ○Li x Ni 0.2 Mn 0.6 O y , where 0.00 ≤ x ≤ 1.52; 1.07 ≤ y < 2.4; Li 1.2 Ni 0.2 Mn 0.6 O2;

[0118] ○LiNi x Co y Mn 1-x-y O2, where 0 ≤ x and y ≤ 0.5; LiNi x Ce z Co y Mn 1-x-y O2, where 0 ≤ x and y ≤ 0.5 and 0 ≤ z;

[0119] ○Phosphates LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2(PO4)3; Li2MPO4F, where M = Fe, Co, Ni or a mixture of these different elements, LiMPO4F, where M = V, Fe or T or a mixture of these different elements; phosphates of the formula LiMM’PO4, where M and M’ (M ≠ M’) are selected from Fe, Mn, Ni, Co, V, for example LiFex Co 1-x PO4, where 0 < x < 1;

[0120] ○ Iron oxyfluoride 0.9 Co 0.1 OF; LiMSO4F, where M = Fe, Co, Ni, Mn, Zn, Mg;

[0121] ○ 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; Li x V3O8, where 0 < x ≤ 1.7; Li x TiS2, where 0 < x ≤ 1; lithium titanium oxysulfide Li<000009​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​, where 0 ≤ x < 1 and 0 ≤ δ ≤ 2, LiNbO3;

[0127] ○TiNb2O 7±δ ,Li w TiNb2O7, where w ≥ 0,Ti 1-x M 1 x Nb 2-y M 2 y O 7±δ or Li w Ti 1-x M 1 x Nb<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​1-x M 1 x Nb 2-y M 2 y O 7-z M 3 z or Li w Ti 1-x M 1 x Nb 2-y M 2 y O 7-z M 3 z ,in

[0133] ○M 1 and M 2 are at least one element selected from the group consisting of 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,

[0134] ○M 1 and M 2 can be the same as or different from each other,

[0135] ○M 3 is at least one halogen,

[0136] ○ and where 0≤w≤5, 0≤x≤1, 0≤y≤2 and z≤0.3;

[0137] ○TiNb2O 7-z M 3 z or Li w TiNb2O 7-z M 3 z , where M 3 is at least one halogen, preferably selected from F, Cl, Br, I or a mixture thereof, and 0 <z≤0.3;

[0138] ○Ti 1-x Ge x Nb 2-y M 1 y O 7±z , Li w Ti 1-x Ge x Nb 2-y M 1 y O 7±z , Ti1-x Ce x Nb 2-y M 1 y O 7±z , Li w Ti 1- x Ce x Nb 2-y M 1 y O 7±z ,in

[0139] ■M 1 and M 2 are at least one element selected from the group consisting of 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;

[0140] ■0≤w≤5, 0≤x≤1, 0≤y≤2 and z≤0.3;

[0141] ○Ti 1-x Ge x Nb 2-y M 1 y O 7-z M 2 z , Li w Ti 1-x Ge x Nb 2-y M 1 y O 7-z M 2 z , Ti 1-x Ce x Nb 2-y M 1 y O 7-z M 2 z , Li w Ti 1- x Ce x Nb 2-y M 1 y O 7-z M 2 z ,in

[0142] ■M 1 and M 2are at least one element selected from the group consisting of 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, Ce, and Sn,

[0143] ■M 1 and M 2 can be the same as or different from each other,

[0144] ■ and where 0≤w≤5, 0≤x≤1, 0≤y≤2 and z≤0.3;

[0145] ○TiO2;

[0146] ○LiSiTON.

[0147] The porous layer produced using one of these materials according to the present invention can ensure the function of a negative electrode in batteries, especially lithium-ion batteries. For use as a negative electrode in lithium-ion batteries, a negative electrode material with a lithium insertion potential greater than 1 V is advantageously used; this allows the battery to be charged quickly.

[0148] The negative electrode can be made of titanate and / or mixed titanium oxide. The electrodes of the assembly of the present invention are preferably impregnated with an ionic liquid containing a lithium salt. When the ionic liquid includes sulfur atoms, the substrate, which can serve as a current collector, is preferably a precious metal. This type of battery has the advantage of being able to operate at high temperatures.

[0149] The inorganic material E advantageously comprises an electronically insulating material, preferably chosen from:

[0150] ○Al2O3, SiO2, ZrO2, and / or

[0151] o A material selected from the group consisting of lithiated phosphates, preferably selected from the group consisting of: NaSICON type lithiated phosphates, Li3PO4; LiPO3; Li3Al 0.4 Sc 1.6 (PO4)3, called "LASP"; Li 1+x Zr 2-x Ca x (PO4)3, where 0≤x≤0.25; Li 1+ 2x Zr 2-x Ca x (PO4)3, where 0≤x≤0.25, such as Li 1.2 Zr 1.9 Ca 0.1 (PO4)3 or Li 1.4 Zr 1.8 Ca 0.2 (PO4)3;LiZr2(PO4)3;Li 1+3xZr2(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 elements 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 and / or Y; Li 1+x M x (Ga) 2-x (PO4)3, wherein M=Al and / or Y 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 elements; Li 3+y (Sc 2-x M x )Q y P 3-y O 12 , wherein M=Al and / or Y, 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 elements 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 and / or Y, 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 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 elements.

[0152] The porous layer produced using one of these materials according to the present invention can perform the function of a separator in a battery, in particular a lithium-ion battery.

[0153] Another object of the present invention is an assembly consisting of a porous electrode and a porous separator, obtainable by the method for producing an assembly consisting of a porous electrode and a porous separator according to the present invention. This porous assembly advantageously contains no binder. Its porosity is preferably 20% to 60% (by volume), and its pores have an average diameter of less than 50 nm. It can be used as a positive electrode / separator assembly or a negative electrode / separator assembly in an electrochemical device.

[0154] The electrodes of the assembly described herein enable the production of lithium-ion batteries with high energy and power densities. This performance is the result of limited porosity (increasing energy density), a very high specific surface area (favored by the very small size of the electrode's primary particles, which results in an increased exchange surface area and thus reduced ionic resistance), and the absence of organic binders (which would partially block lithium access at the surface of the active material). According to a fundamental feature of the invention, a coating of conductive material is deposited on and within the pores of the porous layer of active material that constitutes the electrode. This coating reduces the battery's series resistance.

[0155] Another object of the present invention is the use of the method for manufacturing an assembly consisting of a porous electrode and a separator according to the present invention for manufacturing an assembly consisting of a porous electrode and a separator in an electronic, electrical, or electrochemical device. These devices are selected from the group consisting of: lithium-ion batteries with a capacity greater than 1 mAh; sodium-ion batteries; lithium-air batteries; photovoltaic cells; and fuel cells.

[0156] Another object of the present invention is to manufacture a battery, implementing the method for manufacturing an assembly consisting of a porous electrode and a separator according to the present invention, or implementing the method for manufacturing an assembly consisting of a porous electrode and a separator according to the present invention. The battery is preferably a lithium-ion battery. In particular, this method for manufacturing an assembly consisting of a porous electrode and a separator can be implemented to manufacture an assembly in which the porous electrode is the positive electrode or the negative electrode. This method for manufacturing a battery may comprise a step in which the assembly consisting of a porous electrode and a separator is impregnated with an electrolyte, preferably a phase containing lithium ions, the electrolyte being selected from the group consisting of:

[0157] an electrolyte consisting of at least one aprotic solvent and at least one lithium salt;

[0158] An electrolyte consisting of at least one ionic liquid or poly(ionic) liquid and at least one lithium salt;

[0159] ○ A mixture of an aprotic solvent and an ionic liquid or a poly(ionic) liquid and a lithium salt;

[0160] o ion-conducting polymers produced by the addition of at least one lithium salt; and

[0161] ○ Ion-conducting polymers made by incorporating liquid electrolytes into the polymer phase or mesoporous structure.

[0162] The ionic liquids can be salts that melt at room temperature (these products are called RTILs - room temperature ionic liquids) or ionic liquids that are solid at room temperature. These ionic liquids that are solid at room temperature must be heated to liquefy them so that they can be impregnated into the electrodes; they solidify in the porous layer.

[0163] A final object of the present invention is an electrochemical device selected from the group consisting of: lithium-ion batteries with a capacity greater than 1 mAh; sodium-ion batteries; lithium-air batteries; photovoltaic cells; fuel cells, which can be obtained by the manufacturing method according to the present invention. DETAILED DESCRIPTION

[0164] 1. Definition

[0165] In this document, the size of a particle is defined by its largest dimension. "Nanoparticle" means any particle or object of nanometer size having at least one dimension less than or equal to 100 nm.

[0166] An "ionic liquid" is any liquid salt capable of transporting electrical energy. Unlike all molten salts, it melts at temperatures below 100°C. Some of these salts remain liquid at room temperature and do not solidify even at extremely low temperatures. Such salts are known as "room-temperature ionic liquids."

[0167] The term "mesoporous" material refers to any solid having so-called "mesopores" within its structural pores, 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 corresponds to the terminology used 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 defined above have nanometer dimensions within the meaning of the definition of nanoparticles, it should be understood that pores smaller than mesopores are referred to as "micropores" by those skilled in the art.

[0168] 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”; this article also introduces porosity characterization techniques, in particular the BET method.

[0169] Within the meaning of the present invention, a "mesoporous layer" is 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 mesopore porosity greater than X vol%" used in the following description and applies to the porous electrodes and separators used in the components according to the present invention.

[0170] According to the IUPAC definition, the term "aggregate" refers to a weakly bound 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) under the action of ultrasound and become primary nanoparticles suspended in a liquid phase.

[0171] According to the IUPAC definition, the term "agglomerate" refers to a strongly bound grouping of primary particles or aggregates.

[0172] 2. Preparation of Nanoparticle Suspension

[0173] The methods for preparing the porous electrodes and separators of the present invention start with nanoparticle suspensions. These nanoparticle suspensions are preferably not prepared from dry nanopowders. They can be prepared by grinding powders or nanopowders in a liquid phase and / or by using ultrasonic treatment to deagglomerate the nanoparticles.

[0174] In another embodiment of the present invention, a nanoparticle suspension is prepared directly by precipitation. Synthesizing nanoparticles by precipitation yields primary nanoparticles of very uniform size, with a unimodal size distribution, i.e., a very tight and monodisperse distribution, and good crystallinity and purity. Using these very uniform, narrowly distributed nanoparticles, a porous structure with controlled, open porosity can be obtained after deposition. The porous structure obtained after deposition of these nanoparticles has very few, and preferably no, closed pores.

[0175] In a more preferred embodiment of the present invention, the nanoparticles are prepared directly in their initial size by hydrothermal or solvent thermal synthesis; this method allows to obtain nanoparticles with a very narrow size distribution, which are called "monodisperse nanoparticles". The size of these non-aggregated or non-agglomerated nanopowders / nanoparticles is called the initial size. The initial size is usually between 2 nm and 150 nm. The initial size is preferably between 10 nm and 50 nm, preferably between 10 nm and 30 nm; this size promotes in the subsequent method steps the formation of an interconnected mesoporous network due to the "necking" phenomenon. The electronic and ionic conduction of the porous electrode according to the present invention occurs due to the "necking" phenomenon that forms the interconnected mesoporous network.

[0176] In an advantageous embodiment, the suspension of monodisperse nanoparticles is carried out in the presence of a ligand or an organic stabilizer, thereby avoiding aggregation or even agglomeration of the nanoparticles. A binder can also be added to the nanoparticle suspension to promote the formation of a deposition or primary strip, in particular a thick, crack-free deposition. In fact, in the context of the present invention, it is preferred to start with a suspension of non-agglomerated primary particles and then induce or cause agglomeration in the suspension, rather than allowing the primary particles to spontaneously agglomerate during the suspension preparation stage.

[0177] This monodisperse nanoparticle suspension can be purified to remove any potentially interfering ions. Depending on the degree of purification, it can be subjected to special treatments to form aggregates or agglomerates of controlled size. More specifically, the formation of aggregates or agglomerates can be caused by instability of the suspension, particularly due to ions, the addition of dry extracts of the suspension, changes in the suspension solvent, and the addition of destabilizing agents. If the suspension is completely purified, it is stable and can be destabilized by adding ions, usually in the form of salts; these ions are preferably lithium ions (preferably added in the form of LiOH).

[0178] If the suspension is not completely purified, aggregates or agglomerates may form spontaneously or upon aging. This approach is simpler because it involves fewer purification steps, but the size of the aggregates or agglomerates is more difficult to control. A fundamental aspect of manufacturing the component electrodes and separators of the present invention is to appropriately control the size of the primary particles of the electrode material P and / or the inorganic material E and their degree of aggregation or agglomeration.

[0179] If stabilization of the nanoparticle suspension occurs after agglomerate formation, they will remain in the form of agglomerates; the resulting suspension can be used to prepare mesoporous deposits.

[0180] This suspension of nanoparticle aggregates or agglomerates is then used to deposit porous (preferably mesoporous) electrode layers and inorganic layers (i.e., the membrane of the component described in the present invention) by electrophoresis, inkjet printing, flexographic printing, doctor blade coating, roller coating, curtain coating, extrusion slot coating, dip coating or casting.

[0181] According to the applicant's observations, when the nanoparticle aggregates or agglomerates have an average diameter between 80 and 300 nm, preferably between 100 and 200 nm, a mesoporous layer having an average mesopore diameter between 2 and 50 nm is obtained in a subsequent step of the process.

[0182] The porous electrode layer of the component described in the present invention and the corresponding inorganic layer corresponding to the separator can be deposited from a suspension with a relatively high concentration of aggregates or agglomerates of nanoparticles containing active material P or corresponding inorganic material E by dip coating, inkjet printing, roller coating, curtain coating or doctor blade coating.

[0183] For the electrophoretic method, a suspension containing nanoparticle agglomerates of active material P or corresponding inorganic material E at a lower concentration is used to produce the porous electrode layer of the component according to the invention or, respectively, the inorganic layer corresponding to the separator.

[0184] The method for depositing nanoparticle aggregates or agglomerates by electrophoresis, dip coating, inkjet printing, roller coating, curtain coating or blade coating is simple, safe, easy to implement and industrialized, and can obtain final uniform porous layer. Electrophoretic deposition is a technology that can uniformly deposit over a large area at a high deposition rate. Compared with electrophoretic deposition technology, coating methods, particularly dip coating, roller coating, curtain coating or blade coating, can simplify the management of baths. Inkjet printing deposition allows localized deposition.

[0185] The porous layer produced from a thick layer or the separator produced from a thick layer can be produced in one step by roller coating, curtain coating, slot coating or blade coating (ie using a doctor blade).

[0186] It is noteworthy that the colloidal suspensions in water and / or ethanol and / or IPA and mixtures thereof exhibit improved fluidity compared to suspensions obtained in NMP. Consequently, the dry extract content of the nanoparticle agglomerate suspension can be increased. These agglomerates are preferably less than or equal to 200 nm in size and have a polydisperse size, even comprising two populations of particles of different sizes.

[0187] The formulation of inks and pastes for producing electrodes is simplified compared to existing technologies. The risk of carbon black agglomeration in the suspension does not increase when the dry extract content is increased.

[0188] The production of the assembly of the porous electrode and the separator according to the invention will be described below.

[0189] 3. Layer deposition and consolidation

[0190] In general, a layer of a nanoparticle suspension is deposited on the substrate by any suitable method, in particular by a method selected from the group consisting of electrophoresis, printing (preferably inkjet printing and flexographic printing), and coating (preferably knife coating, roller coating, curtain coating, dip coating or slot coating); the suspension is usually in the form of an ink, that is to say a liquid with relatively good fluidity, but can also be in the form of a paste. The deposition technique and the method of deposition must be compatible with the viscosity of the suspension, and vice versa.

[0191] The deposited layer is then dried. The deposited layer is then consolidated to obtain the desired mesoporous ceramic structure. This consolidation will be described below. Consolidation can be carried out by heat treatment, mechanical treatment followed by heat treatment, and optionally thermomechanical treatment (usually hot pressing). During this thermomechanical or thermal treatment process, the electrode layer will be free of any organic components and organic residues (such as the liquid phase of the nanoparticle suspension and any surfactant products): it will become an inorganic (ceramic) layer. The consolidation of the plate is preferably carried out after it has been separated from the intermediate substrate, as the latter is at risk of degradation during this treatment process.

[0192] The deposition, drying and consolidation of the layers may present some problems which will now be discussed. These problems are partly related to the fact that during the consolidation of the layers, shrinkage occurs, which generates internal stresses.

[0193] 3.1 Substrates that can be used as current collectors

[0194] According to a first embodiment, each layer of electrode is deposited on a substrate that can be used as a current collector. By means of the above-mentioned deposition technique, a layer comprising a nanoparticle suspension or nanoparticle agglomerates can be deposited on both sides. The substrate is used as the current collector in the battery of the porous electrode of the present invention, and it can be a metal, such as a metal strip (i.e., a rolled metal sheet). The substrate is preferably selected from the alloy strips of two or more materials of tungsten, molybdenum, chromium, titanium, tantalum, stainless steel or these materials. Not too expensive substrates, such as copper or nickel, can accept conductive and anti-oxidation protective coatings.

[0195] The metal plate can be coated with a layer of noble metal, in particular selected from gold, platinum, palladium, titanium or an alloy mainly containing at least one or more of these metals, or coated with a layer of ITO type conductive material (which can advantageously act as a diffusion barrier).

[0196] Generally speaking, a substrate that can act as a current collector must be able to withstand the thermal processing conditions of the deposited layers and the operating conditions within the battery cell. Therefore, copper and nickel are suitable for contact with the anode material; they may oxidize the cathode.

[0197] For layer deposition, electrophoresis methods can be used (especially in water). In this particular case, the substrate undergoes electrochemical polarization, which causes it to oxidize or dissolve in the nanoparticle suspension. In this case, only substrates that are free of anodic oxidation and / or corrosion can be used. This is particularly true for stainless steel and precious metals.

[0198] When the deposition of nanoparticles and / or agglomerates is carried out by one of the other techniques mentioned below (e.g., coating, printing), the choice of substrate is expanded. The choice is then based on the stability of the metal under the conditions of the electrode operating potential and in contact with the electrolyte. However, depending on the synthetic route used to produce the nanoparticles, more or less aggressive heat treatments are necessary to achieve consolidation and possible recrystallization of the nanopowder: this aspect will be further explored in Section 5 below.

[0199] In all cases, to obtain these mesoporous electrodes, a consolidation heat treatment is necessary. The substrate, capable of acting as a current collector, must be able to withstand these heat treatments without oxidizing. Several strategies can be employed.

[0200] When the nanopowder deposited on the substrate by inking is amorphous and / or has many point defects, a heat treatment is necessary. In addition to consolidation, this allows the material to recrystallize in the correct crystalline phase and stoichiometric ratio. To achieve this, a heat treatment at temperatures between 500 and 700°C is typically required. The substrate must withstand this type of heat treatment, and materials capable of withstanding these high temperatures must be used. For example, strips of stainless steel, titanium, molybdenum, tungsten, tantalum, chromium, and their alloys can be used.

[0201] When the nanopowders and / or agglomerates are crystallized, nanopowders and agglomerates having the correct phase and crystal structure are obtained by hydro-solvothermal synthesis, and then a consolidation heat treatment can be carried out under a controlled atmosphere. This allows the use of less expensive substrates, such as nickel, copper, and aluminum. Due to the very small size of the primary particles obtained by hydrothermal synthesis, the temperature of the consolidation heat treatment can be reduced to approximately 350-500°C and / or the duration of the consolidation heat treatment can be shortened, which also broadens the range of substrate choices. However, these less expensive substrates must be able to withstand heat treatment in order to remove organic additives that may be contained in the nanoparticle suspension used, such as ligands, stabilizers, binders, or residual organic solvents (degreasing). It is advantageous for this heat treatment to be carried out under an oxidizing atmosphere.

[0202] Pseudo-hydrothermal synthesis may also produce amorphous nanoparticles that require subsequent recrystallization.

[0203] These substrates, which can act as current collectors, can optionally be coated with a conductive oxide thin film. This oxide may have the same composition as the electrode. These thin films can be prepared using a sol-gel method. This oxide-based interface can limit substrate corrosion and provide a better connection between the electrode and the substrate.

[0204] Regarding the operating conditions within the battery cell, it should first be noted that in batteries using the porous electrodes described in the present invention, the liquid electrolyte impregnating the porous electrodes is in direct contact with the substrate that can act as a current collector. However, when these electrolytes are in contact with the substrate that can act as a current collector, that is, when the substrate is metallic and polarized at a potential that is extremely positive for the cathode and extremely negative for the anode, these electrolytes can induce the current collector to dissolve. These parasitic reactions shorten the battery life and accelerate the self-discharge of the battery. To avoid this, the cathode of all lithium-ion batteries uses a substrate that can act as a current collector, such as an aluminum current collector. Aluminum has the property of being anodized at extremely positive potentials, so the oxide layer formed on the aluminum surface prevents the aluminum from dissolving. However, the melting temperature of aluminum is close to 600°C, and if the electrode consolidation process could melt the current collector, aluminum cannot be used to manufacture the battery of the present invention.

[0205] Therefore, to avoid parasitic reactions that could shorten the battery's life and accelerate its self-discharge, titanium strips are preferably used as the cathode current collector. During battery operation, the titanium strips (like aluminum) will be anodized, and their oxide layer will prevent the parasitic reaction of titanium dissolution when in contact with the liquid electrolyte. Furthermore, because titanium has a much higher melting point than aluminum, the all-solid-state electrodes of the present invention can be manufactured directly on such strips.

[0206] The use of these bulk materials, in particular titanium strips, also makes it possible to protect the cut edges of the battery electrodes from corrosion phenomena. The use of copper strips advantageously makes it possible to protect the cut edges of the battery anodes from corrosion phenomena.

[0207] Stainless steel can also be used as a current collector, especially when it contains titanium or aluminum as alloying elements, or has a thin layer of protective oxide.

[0208] Other substrates acting as current collectors may be used, such as less noble metal strips covered with a protective coating to avoid possible dissolution of these strips due to the presence of electrolyte in contact.

[0209] These less noble metal strips may be copper, nickel or metal alloy strips, such as stainless steel strips, Fe-Ni alloy strips, Be-Ni-Cr alloy strips, Ni-Cr alloy strips or Ni-Ti alloy strips.

[0210] The coatings that can be used to protect substrates used as current collectors can be of different natures. The coatings can be:

[0211] A thin layer of the same electrode material obtained by the sol-gel method. The film is non-porous, preventing contact between the electrolyte and the metal current collector;

[0212] a thin layer obtained by vacuum deposition of the same material as the electrode, in particular physical vapor deposition (PVD) or chemical vapor deposition (CVD);

[0213] A dense, defect-free, thin metal layer, for example of gold, titanium, platinum, palladium, tungsten, or molybdenum. These metals can be used to protect the current collector because they have good electrical conductivity and can withstand the heat treatments during the subsequent electrode manufacturing process. This layer can be produced, inter alia, by electrochemical, PVD, CVD, evaporation, ALD, and other methods;

[0214] ●Thin carbon layers, such as diamond and graphite carbon, deposited by ALD, PVD, CVD or inking from sol-gel solutions can be heat treated to obtain a carbon-doped inorganic phase that makes it conductive.

[0215] Conductive or semiconducting oxide layers, such as ITO (indium tin oxide), are deposited only on the cathode substrate because the oxide is reduced at low potentials;

[0216] • A conductive nitride layer, such as a TiN layer, is deposited only on the cathode substrate, since nitrides intercalate lithium at low potentials.

[0217] Coatings useful for protecting substrates used as current collectors must be electronically conductive so as not to interfere with the operation of electrodes subsequently deposited thereon due to excessive electrical resistance.

[0218] Generally speaking, in order not to seriously affect the operation of the battery cell, the maximum dissolution current (unit: μA / cm 2 ) must be greater than the electrode surface capacity (unit: μAh / cm2 ) is 1000 times lower.

[0219] When attempts are made to increase the electrode thickness, it is observed that the shrinkage caused by consolidation can lead to cracking of the layer or the generation of shear stresses at the interface between the substrate (with fixed dimensions) and the ceramic electrode. When this shear stress exceeds a threshold, the layer detaches from the substrate.

[0220] In order to avoid this phenomenon, it is preferred to increase the thickness of the electrode by a series of deposition-sintering operations. The first variation of the first embodiment of the deposited layer has obtained good results, but productivity is not very high. Or, in the second variation, thicker layers are deposited on the two sides of the perforated substrate. These holes must have a sufficiently large diameter so that the two layers before and after contact at the hole. Therefore, in the consolidation process, nanoparticles and / or nanoparticle agglomerates of the electrode material contacted by the hole in the substrate join together to form a junction (junction between two surface depositions). This limits the adhesion loss of each layer and the substrate in the consolidation step.

[0221] In order to avoid this phenomenon, i.e. to increase the deposit thickness while limiting or eliminating the appearance of cracks, binders and dispersants can be added. These additives and organic solvents can be removed during the sintering process by heat treatment or during a heat treatment carried out before the sintering process, preferably under oxidizing atmosphere conditions (for example by degreasing).

[0222] 3.2 Intermediate substrate

[0223] According to a second embodiment, the electrode layers are not deposited on a substrate that can serve as a current collector, but on an intermediate temporary substrate. In particular, relatively thick layers (called "green sheets") can be deposited from a suspension of nanoparticles and / or nanoparticle agglomerates with a higher concentration (i.e., a less fluid, preferably pasty) . These thick layers are deposited, for example, by coating, preferably by blade coating (a technique known in the term "casting") or slot coating. The intermediate substrate can be a polymer plate, for example polyethylene terephthalate, PET for short. During the drying process, these layers do not crack, in particular when dried after the layer obtained in step (b) is separated from its intermediate substrate. For thermal consolidation (preferably already dried), it can be separated from the substrate; thus, after cutting the electrode, called the "raw" electrode, a plate can be obtained, which, after a calcination heat treatment and partial sintering, will give a mesoporous self-supporting ceramic plate.

[0224] A three-layer stack is then formed, i.e., two electrode plates of the same polarity are separated by a conductive plate (e.g., a metal plate or a graphite plate) that can act as a current collector. The stack is then assembled by thermomechanical treatment (comprising pressing and heat treatment, preferably performed simultaneously). Alternatively, in order to facilitate bonding between the ceramic plate and the metal plate, a layer allowing conductive bonding can be coated on the interface. This layer can be a sol-gel layer (preferably a type that allows the electrode chemical composition to be obtained after heat treatment), which may contain particles of conductive material, which will form a ceramic bond between the mesoporous electrode and the metal plate. The layer can also consist of a thin layer of non-sintered electrode nanoparticles, or a thin layer of conductive glue (e.g., containing graphite particles), or a metal layer of a low melting point metal.

[0225] When the conductive plate is a metal, it is preferably a rolled plate, i.e., a plate obtained by rolling. Rolling may optionally be followed by a final annealing, which, in metallurgical terms, may be a (full or partial) softening or recrystallization annealing. Electrochemically deposited plates, such as electrodeposited copper plates or electrodeposited nickel plates, may also be used.

[0226] In any case, it is possible to obtain mesoporous ceramic electrodes free of organic binders, located on either side of a metal substrate serving as current collector.

[0227] 4. Deposition of active material P layer

[0228] Generally, as previously described, the electrodes of the present invention can be made from nanoparticle suspensions using known coating techniques. These techniques are the same as the printing and coating methods described above in the section entitled "Preparation of Nanoparticle Suspensions."

[0229] For all these techniques, it is advantageous for the suspension to have a dry extract of greater than 20%, preferably greater than 40%; this reduces the risk of cracking during drying.

[0230] Electrophoresis can also be used.

[0231] In a first embodiment, the method of the present invention advantageously uses electrophoresis of a nanoparticle suspension as a technique for depositing a porous (preferably mesoporous) electrode layer. Methods for depositing electrode layers from nanoparticle suspensions are well known (see, for example, EP 2774194 B1). The substrate can be a metal, such as a metal plate. The substrate used as a current collector in a battery using the porous electrode of the present invention is preferably selected from titanium, copper, stainless steel, or molybdenum strips.

[0232] For example, a stainless steel plate with a thickness of 5 μm can be used. The metal plate can be coated with a layer of a noble metal, in particular an alloy selected from gold, platinum, palladium, titanium, or mainly containing at least one or more of these metals, or coated with a layer of an ITO type conductive material (which has the advantage of being able to serve as a diffusion barrier layer).

[0233] In certain embodiments, a layer of electrode material, preferably a thin layer, is deposited on the metal layer. This deposition must be very thin (typically tens of nanometers, more typically between 10 nm and 100 nm). This can be done by a sol-gel process. For example, LiMn2O4 can be used for a porous LiMn2O4 cathode.

[0234] To perform electrophoresis, a counter electrode is placed in the suspension and a voltage is applied between the conductive substrate and the counter electrode.

[0235] In an advantageous embodiment, the electrophoretic deposition of aggregates or agglomerates of nanoparticles is carried out by pulsed-mode constant-current electrodeposition; high-frequency current pulses are used, which avoids the formation of bubbles on the surface of the deposited layer and variations in the electric field in the suspension during deposition. Thus, the thickness of the layer deposited by electrophoretic deposition, preferably by pulsed-mode constant-current electrodeposition, is advantageously less than 10 μm, preferably less than 8 μm, and even more preferably between 1 μm and 6 μm.

[0236] In another embodiment, no matter the chemical property of the nanoparticles adopted, the aggregate or agglomerate of the nanoparticles can be deposited by dip coating. When the nanoparticles used have little or no charge, this deposition method is preferably adopted. In order to obtain a layer of desired thickness, the step of depositing the nanoparticle aggregate or agglomerate by dip coating is repeated if necessary, and the step of drying the resulting layer is then repeated. In order to increase the thickness of the crack-free layer, it is advantageous to use at least one organic additive in the colloidal suspension or the deposition paste, for example a part, a stabilizer, a thickening agent, a bonding agent or a residual organic solvent.

[0237] 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.

[0238] 5. Consolidation treatment of sedimentary layer

[0239] The electrode layer is consolidated.

[0240] The deposited layer must be dried; drying must not lead to crack formation. Therefore, it is preferred to carry out the process under controlled humidity and temperature conditions or to use colloidal suspensions and / or pastes that, in addition to aggregates or agglomerates of monodisperse primary nanoparticles, also contain at least one electrode active material P according to the invention, organic additives (e.g. ligands, stabilizers, thickeners, binders or residual organic solvents) to produce the porous layer.

[0241] The dried layer can be consolidated by a pressing and / or heating step (thermal treatment). In a very advantageous embodiment of the invention, this treatment leads to a partial coalescence of the primary nanoparticles in the aggregates or agglomerates as well as between adjacent aggregates or agglomerates; this phenomenon is called "necking" or "neck formation". It is characterized by the partial coalescence of two contacting particles, which remain separated but are connected by a (contracted) neck. Lithium ions and electrons can move within these necks and can diffuse between particles without encountering particle boundaries. The nanoparticles are linked together, ensuring the conduction of electrons from one particle to another. Thus, a three-dimensional network of interconnected particles with high ion mobility and electronic conduction is formed; this network includes pores (preferably mesopores) in which the particle concept disappears after the thermal treatment.

[0242] The temperature required to achieve "necking" depends on the material; the treatment time is temperature-dependent, given the diffusion nature of the necking phenomenon. This process, which can be called sintering, produces varying degrees of pronounced coalescence (necking), depending on its duration and temperature, which has an impact on porosity. Thus, it is possible to reduce the porosity to 30% (or even 25%) while maintaining perfectly uniform channel dimensions.

[0243] The heat treatment can also be used to remove organic additives that may be present in the nanoparticle suspension used, such as ligands, stabilizers, binders, or residual organic solvents. According to another variant, an additional heat treatment can be carried out in an oxidizing atmosphere to remove these organic additives that may be present in the nanoparticle suspension used. This additional heat treatment is advantageously carried out before the consolidation treatment in step c), in order to obtain a porous (preferably mesoporous) layer.

[0244] 6. Deposition of conductive material coating

[0245] According to an essential characteristic of the invention, a coating of electrically conductive material is deposited on and in the pores of the porous layer, thereby obtaining the porous electrode of the assembly according to the invention.

[0246] In fact, as mentioned above, no organic binder is required and the method described in the present invention, which necessarily involves a step of depositing agglomerated nanoparticles of electrode material (active material), allows the nanoparticles to naturally "bond" to each other, generating a rigid porous three-dimensional structure after consolidation (e.g. annealing); this porous (preferably mesoporous) layer is perfectly suitable for surface treatment by gases or liquids penetrating into the open porous structure of said layer.

[0247] Very advantageously, this deposition is carried out by a technique that allows encapsulating the coating (also called "conformal deposition"), that is, it faithfully reproduces the atomic topography of the substrate on which it is deposited, penetrating into the open pore network of the layer. The conductive material may be carbon.

[0248] Familiar techniques such as ALD (atomic layer deposition) or CSD (chemical solution deposition) may be suitable for this deposition. They can be applied to the porous layer after fabrication, before separator particle deposition, and before battery assembly. ALD deposition proceeds layer by layer in a cyclical process and produces an encapsulating coating that faithfully replicates the substrate topography; the coating covers the entire electrode surface. The thickness of the encapsulating coating is typically between 1 nm and 5 nm.

[0249] The temperature of ALD deposition is typically between 100°C and 300°C. It is important that the layers do not contain organic materials: they must not contain any organic binders, and any residues of stabilizing ligands used to stabilize the suspension must be removed by purification of the suspension and / or during heat treatment of the dried layer. In fact, at the temperatures of ALD deposition, there is a risk that organic materials forming organic binders (for example, polymers contained in electrodes produced by ink casting) will decompose and contaminate the ALD reactor. In addition, the presence of residual polymer in contact with the particles of the electrode active material will prevent the ALD coating from encapsulating all the particle surfaces, thereby reducing its effectiveness.

[0250] CSD deposition technology also allows the production of an encapsulating coating using precursors of an electronically conductive material that faithfully reproduces the topography of the substrate; it covers the entire surface of the electrode. The thickness of the encapsulating coating is typically less than 5 nm, preferably between 1 nm and 5 nm. It must then be converted into an electronically conductive material. In the case of carbon precursors, this is achieved by pyrolysis, preferably under an inert gas such as nitrogen.

[0251] In this variant of depositing the nanolayer of electronically conductive material, the diameter D of the primary particles of the electrode material is preferably 50 It is at least 10 nm to prevent the conductive layer from blocking the open pores of the layer.

[0252] 7. Fabrication of a diaphragm (inorganic material E layer) on a porous electrode

[0253] Preferably after drying, at least one layer of an inorganic material E from a suspension of nanoparticles of an inorganic material E is deposited on a porous (preferably mesoporous) electrode comprising a coating of a conductive material using the known coating techniques described above in paragraph 4. Methods for depositing porous inorganic layers from nanoparticle suspensions are well known (see, for example, WO 2019 / 215411 A1).

[0254] In one embodiment, the materials used to make the porous layer of the separator according to the present invention are selected from low-melting inorganic materials, electronic insulators, and materials that are stable in contact with the electrodes during the hot pressing step. The more refractory the material, the more necessary it is to heat the electrode / electrolysis separator interface at high temperatures, which runs the risk of modifying the electrode material interface (particularly through interdiffusion), which can lead to parasitic reactions and the creation of a depletion layer with electrochemical properties different from those of the same material further away from the interface. Lithium-containing materials are preferred because they can prevent or even eliminate these lithium depletion phenomena.

[0255] The material used to make the porous inorganic layer of the present invention may be an ion-conducting material, such as a solid electrolyte containing lithium, to avoid the formation of a lithium-depleted region at the electrode / electrolysis membrane interface. The inorganic material E preferably comprises an electronically insulating material, preferably a material selected from the group consisting of lithiated phosphates, preferably selected from the group consisting of: NaSICON type lithiated phosphates, Li3PO4; LiPO3; Li3Al 0.4 Sc 1.6 (PO4)3, called "LASP"; Li 1+x Zr 2-x Ca x (PO4)3, where 0≤x≤0.25; Li 1+2x Zr 2-x Ca x (PO4)3, where 0≤x≤0.25, such as Li 1.2 Zr 1.9 Ca 0.1 (PO4)3 or Li 1.4 Zr 1.8 Ca 0.2 (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 elements 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 and / or Y; Li 1+x M x (Ga) 2-x (PO4)3, wherein M=Al and / or Y 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 elements; 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 elements 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 and / or Y, 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 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 elements. Li3PO4 is particularly preferred.

[0256] The inorganic layer is a porous (preferably mesoporous) ceramic membrane that performs an electrolyte separation function. The ceramic nanoparticles used to make the component separator of the present invention must be electrochemically stable and electronically insulating when in contact with the electrode, preferably having lithium ion conductivity. Depositing this inorganic layer (mesoporous ceramic membrane) can reduce the thickness of the electrolyte membrane. This layer has excellent mechanical properties. This reduction in thickness increases the volumetric energy density of the battery.

[0257] The all-ceramic and / or glass-ceramic nature of this porous inorganic layer, devoid of organic elements, ensures good mechanical strength, complete wetting by liquid electrolytes, even room-temperature ionic liquids, and also ensures battery operation over a very wide temperature range (without the risk of separator melting and / or rupture).

[0258] Fabricating the porous inorganic layer, or rather the separator, on the porous electrode remains difficult to achieve. Indeed, the performance of the porous electrodes of the present invention stems in part from the fact that their surfaces are coated with a conductive material (e.g., carbon). However, the deposited agglomerates of inorganic nanoparticles E, which ensure the electrolytic separation function, are enriched with organic material after deposition. These organic materials are present in the solvent adsorbed on the nanoparticle surfaces and in the organic stabilizer used in the formulation of the inorganic nanoparticle E suspension. Therefore, before impregnating the assembly of the porous electrode and separator of the present invention, these organic residues must be removed from the separator. To achieve this, a calcination treatment is necessary. This calcination treatment is performed by annealing in air, thereby converting these organic materials into CO2 and removing them. However, to maintain the performance of the porous electrode associated with the ceramic separator, the organic material calcination treatment must not remove the conductive material coating (e.g., carbon coating) on ​​the porous electrode surface. To this end, the applicant has identified treatment conditions that remove the organic material while maintaining the conductive material coating (e.g., carbon coating) on ​​the porous electrode, without any carbon deposits in the separator that could impair the battery's electrical insulation, particularly its self-discharge.

[0259] This heat treatment is carried out in air at a moderate temperature to remove organic matter contained in the electrolytic diaphragm deposit in the form of CO2 while maintaining the conductive material coating (e.g., carbon coating) on ​​the surface of the porous electrode. To this end, the heat treatment should be carried out at a temperature below 500°C, preferably between about 250°C and about 450°C, and most preferably at a temperature below about 400°C.

[0260] After heat treatment, the assembly consisting of the porous electrode and the separator according to the present invention is obtained.

[0261] 8. Use electrolyte to impregnate components to obtain functional components of the battery

[0262] According to a first embodiment of the present invention, the component is impregnated with a polymer containing a lithium salt, so that the polymer is an ion conductor and the ion species transported is lithium ions.

[0263] According to a second embodiment of the invention, the assembly is impregnated with a liquid electrolyte; for example, the electrolyte may be an ionic liquid or an aprotic solvent in which one or more lithium salts are dissolved. Poly(ionic liquids) (PILs) may also be used.

[0264] More specifically, the component according to the invention (before impregnation) is free of organic compounds, and the absence of organic compounds, together with the mesoporous structure, promotes wetting by the lithium-ion-conducting electrolyte. This electrolyte can then be selected without distinguishing it from the group consisting of: an electrolyte consisting of at least one aprotic solvent and at least one lithium salt, an electrolyte consisting of at least one ionic liquid or poly(ionic liquid) and at least one lithium salt, a mixture of an aprotic solvent and an ionic liquid or a poly(ionic liquid) and a lithium salt, an ion-conducting polymer containing at least one lithium salt, or an ion-conducting polymer obtained by adding at least one lithium salt. The polymer is advantageously chosen from poly(ethylene oxide) (often abbreviated to PEO), poly(propylene oxide), polydimethylsiloxane (often abbreviated to PDMS), polyacrylonitrile (often abbreviated to PAN), polymethyl methacrylate (often abbreviated to PMMA), polyvinyl chloride (often abbreviated to PVC), polyvinylidene fluoride (often abbreviated to PVDF), and PVDF-hexafluoropropylene.

[0265] The polymer, whether or not it contains a lithium salt, is generally solid at room temperature and can be melted, and this molten phase can then be impregnated into the pores of the component. After cooling, a component comprising electrodes and a solid electrolyte is obtained.

[0266] This assembly comprising electrodes and solid electrolyte can be used in various ways to produce a basic battery cell.

[0267] 9. Produce basic battery cells using components including porous electrodes and solid electrolytes

[0268] As described above, the assembly of the present invention can be impregnated with a melt phase containing an ion-conducting polymer and, optionally, a lithium salt. After cooling, an assembly comprising a porous electrode and a solid electrolyte is obtained. This assembly comprising electrodes and a solid electrolyte can be used in a variety of ways to produce basic battery cells and, ultimately, batteries.

[0269] This assembly comprising electrodes and a solid electrolyte can be connected to:

[0270] - another component comprising an electrode and a solid electrolyte, or

[0271] - dense electrodes, or

[0272] - previously used polymer-impregnated porous electrodes, or

[0273] - a dense electrode previously covered with a layer of electrolyte, or

[0274] - The porous electrode, previously covered with a porous electrolyte, is impregnated with a polymer.

[0275] The resulting stack is then hot-pressed to assemble the battery's basic cell. During the hot-pressing process, the impregnated ion-conducting polymer softens, allowing the assembly of the components, including the electrodes and solid electrolyte, and their connected subsystems.

[0276] To ensure reliable bonding between the assembly comprising electrodes and solid electrolytes and its connected subsystems during hot pressing, a thin layer of the same ion-conductive polymer used for impregnation of the assembly described herein can be deposited on the assembly comprising electrodes and solid electrolytes and / or its connected subsystems. This can increase the operating temperature range of the final battery.

[0277] For the same purpose, a thin layer of core-shell particles can also be deposited on the assembly comprising the electrode and the solid electrolyte and / or on the subsystems to which it is connected, wherein the core is made of the same inorganic material E as used to make the separator of the assembly according to the invention, and the shell is made of the same ion-conducting polymer used during the impregnation of the assembly according to the invention. This can improve the mechanical properties of the separator and its adhesion to the subsystem to which it is connected.

[0278] The present assembly, comprised of a porous positive electrode and separator impregnated with an ionically conductive polymer, is particularly well-suited for producing batteries with very high energy density using a lithium metal negative electrode. Indeed, to use a lithium metal negative electrode, the battery must be fully solid-state, devoid of liquid electrolyte and / or pockets of liquid electrolyte trapped within polymers or other phases. These liquid phases are specialized areas for lithium metal precipitation.

[0279] In another embodiment, the assembly of the present invention, which is composed of a porous electrode and a separator and impregnated with an ion-conductive polymer containing or not containing a lithium salt, can be connected to the following devices and then assembled:

[0280] - a porous electrode with opposite sign, or

[0281] - a porous electrode of opposite sign covered with a porous membrane, or

[0282] - The assembly of the present invention consisting of a porous electrode and a separator.

[0283] The resulting stack must be assembled by hot pressing. If there is no organic material connecting the different subassemblies, the pressing temperature should be relatively high, preferably above 400°C. In addition, these treatments should be carried out in an inert atmosphere or under vacuum to avoid altering the coating of conductive material present on the porous electrodes of the assembly of the invention. The resulting assembly can subsequently be impregnated with a solid or liquid electrolyte. Impregnation with a solid electrolyte, for example a liquid-phase-free ion-conducting polymer containing a lithium salt, makes it possible to produce batteries that operate with a negative electrode having a low insertion potential without the formation of lithium dendrites.

[0284] Example

[0285] Example 1: Preparation of porous cathode based on LiMn2O4:

[0286] According to the article "A new one pot hydrothermal synthesis and electrochemical characterisation of Li 1+x Mn 2-y O4 spinel structured compounds", Energy & Environmental Science (2010) vol. 3, pp. 1339-1346, a LiMn2O4 nanoparticle suspension was prepared by hydrothermal synthesis: 14.85 g of LiOH·H2O was dissolved in 500 ml of water. 43.1 g of KMnO4 was added to the solution, and the liquid phase was poured into an autoclave. Under stirring, 28 ml of isobutyraldehyde, 25 g / l 40000g / mol polyvinylpyrrolidone (PVP) and water until the total volume reaches 3.54l. Then, the autoclave is heated to 180°C and kept at this temperature for 6 hours. After slow cooling, a black precipitate suspended in the solvent is obtained. The precipitate undergoes a series of centrifugation-water redispersion steps until an aggregate suspension is obtained. The obtained aggregates consist of aggregated primary particles with a size of 10 to 20nm. The obtained aggregates are spherical with an average diameter of about 150nm. The amount of PVP added to the reaction medium can adjust the size and shape of the obtained agglomerates.

[0287] Approximately 10 to 15 wt% of 360,000 g / mol polyvinylpyrrolidone (PVP) is then added to the aqueous suspension of the aggregates. The water is then evaporated until the dry extract of the aqueous suspension of the aggregates is 10%. The ink thus obtained is then applied to a stainless steel bar (316L) with a thickness of 5 μm. The resulting deposit is then dried in an oven at controlled temperature and humidity to prevent crack formation during the drying process. This results in a deposit of approximately 10 μm thickness.

[0288] The resulting deposit was then consolidated at 600°C in air for one hour to bond the nanoparticles together, improve adhesion to the substrate, and complete the recrystallization of the LiMn2O4. The resulting porous film had an open porosity of approximately 45% by volume, with pore sizes ranging from 10 nm to 20 nm.

[0289] The porous membrane was then impregnated with an aqueous sucrose solution of approximately 20 g / l and then annealed at 400° C. under N 2 to obtain a carbon nanocoating on the entire accessible surface of the porous membrane.

[0290] Example 2: Using the electrodes described in Example 1, a porous electrode and integrated electrolytic membrane assembly was manufactured.

[0291] A cathode was prepared as in Example 1. The electrode was covered with a porous layer of a suspension of Li3PO4 nanoparticles as described below.

[0292] Preparation of Li3PO4 nanoparticle suspension

[0293] Prepare two solutions:

[0294] 11.44 g of CH3COOLi·2H2O were dissolved in 112 ml of water, and then 56 ml of water were added to the medium under vigorous stirring to obtain solution A.

[0295] 4.0584 g of H3PO4 was diluted in 105.6 ml of water, and then 45.6 ml of ethanol was added to the solution to obtain a second solution, hereinafter referred to as solution B.

[0296] Solution B was then added to solution A with vigorous stirring.

[0297] 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 1.2 liters of acetone using a homogenizer. A white precipitate was immediately observed suspended in the liquid phase.

[0298] The reaction medium was homogenized for 5 minutes and then kept under magnetic stirring for 10 minutes. The mixture was allowed to stand for 1 to 2 hours. The supernatant was removed and the remaining suspension was centrifuged at 6000 rpm for 10 minutes. 300 ml of water was then added to resuspend the precipitate (using a sonotrode and magnetic stirring). Under vigorous stirring, 125 ml of a 100 g / l sodium tripolyphosphate solution was added to the colloidal suspension thus obtained. The suspension thus became more stable. The suspension was then ultrasonicated using a sonotrode. The suspension was then centrifuged at 8000 rpm for 15 minutes. The precipitate was then redispersed in 150 ml of water. The obtained suspension was then centrifuged again at 8000 rpm for 15 minutes, and the obtained precipitate was redispersed in 300 ml of ethanol to obtain a suspension suitable for electrophoretic deposition.

[0299] Thus, an ethanolic suspension of approximately 100 nm aggregates consisting of 15 nm initial Li3PO4 particles was obtained, with bis(monoacylglycerol)phosphate (BMP for short) as a stabilizer.

[0300] On the previously developed cathode, a porous layer was prepared using the previously described Li3PO4 nanoparticle suspension.

[0301] A thin porous layer of Li3PO4 was then deposited by dip coating from a previously obtained suspension of Li3PO4 nanoparticles containing 20 g / L of agglomerated nanoparticles at a deposition rate of approximately 10 mm / s. This produced a layer approximately 3 to 4 μm thick on the electrode. The layer was then dried in air at 120°C, and then calcined at approximately 350 to 400°C for 60 minutes to remove all traces of organic residues from the separator while preserving the carbon nanocoating of the porous electrode.

Claims

1. A method of manufacturing an electrochemical device selected from the group consisting of a lithium-ion battery, a sodium-ion battery, a lithium-air battery, a photovoltaic cell, and a fuel cell. The method implements a method for producing an assembly consisting of a porous electrode and a porous separator, The electrode comprises a porous layer deposited on a substrate, the layer being binder-free, having a porosity between 20% and 60% by volume, and having an average pore diameter of less than 50 nm, The separator comprises a porous inorganic layer deposited on the electrode, the porous inorganic layer being binder-free, having a porosity between 25% and 60% by volume, and an average pore diameter of less than 50 nm. The manufacturing method is characterized in that: (a) providing a substrate, a first colloidal suspension or paste comprising monodisperse aggregates or agglomerates of primary nanoparticles of at least one active electrode material P, the average primary diameter D of the primary nanoparticles being 50 The average diameter D of the aggregates or agglomerates is between 2 nm and 150 nm. 50 is between 50 nm and 300 nm, and a second colloidal suspension comprising aggregates or agglomerates of nanoparticles of at least one inorganic material E, said nanoparticles having an average primary diameter D 50 The average diameter D of the aggregates or agglomerates is between 2 nm and 100 nm. 50 is between 50 nm and 300 nm; (b) depositing a layer of the colloidal suspension or paste provided in step (a) on at least one surface of the substrate; (c) drying the layer obtained in step (b) and consolidating it by compression and / or heating to obtain a porous inorganic layer before or after separating the layer from its intermediate substrate; (d) depositing a coating of a conductive material on and within the pores of the porous layer to form the porous electrode; (e) depositing a porous inorganic layer on the porous electrode obtained in step (d) using the second colloidal suspension provided in step (a) by a technique selected from the group consisting of: electrophoresis, printing, and coating; (f) drying the porous inorganic layer of the structure obtained in step (e) and heat-treating it at a temperature below 500° C. to obtain the assembly consisting of a porous electrode and a porous separator, The substrate is a substrate or an intermediate substrate capable of serving as a current collector.

2. The method according to claim 1, characterized in that The specific surface area of ​​the porous layer obtained at the end of step (c) is 10 m 2 / g and 500 m 2 / g.

3. The method according to claim 1 or 2, characterized in that The thickness of the porous layer obtained at the end of step (c) is between 4 μm and 400 μm.

4. The method according to claim 1, wherein When the substrate is an intermediate substrate, the layer is separated from the intermediate substrate in step (c) before or after drying to form a porous plate.

5. The method according to claim 1, wherein When the colloidal suspension or paste provided in step (a) contains organic additives, the layer dried in step c) of claim 1 and / or the porous plate of claim 4 is subjected to a heat treatment.

6. The method according to claim 1, wherein The thickness of the porous inorganic layer obtained at the end of step (f) is between 3 μm and 20 μm.

7. The method according to claim 1, characterized in that The conductive material is carbon.

8. The method according to claim 1, characterized in that The deposition of the coating of conductive material can be carried out by atomic layer deposition techniques or by immersing the layer in a liquid phase comprising a precursor of the conductive material and then converting the precursor into the conductive material.

9. The method according to claim 8, characterized in that The precursor is a carbon-rich compound and is characterized in that the conversion into the conductive material is accomplished by pyrolysis.

10. The method according to claim 1, wherein the material P is 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, wherein X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earth elements, wherein 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 elements, 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; Li x M y O2, wherein 0.6≤y≤0.85; 0≤x+y≤2; M is selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn and Sb or a mixture of these elements; Li 1.20 Nb 0.20 Mn 0.60 O2; Li 1+x Nb y Me z A p O₂, where Me is at least one transition metal selected from: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs and Mt, where 0.6 < x < 1; 0 < y < 0.5; 0.25 ≤ z < 1; where A ≠ Me and A ≠ Nb, and 0 ≤ p ≤ 0.2; Li x Nb y-a N a M z-b P b O 2-c F c , where 1.2 < x ≤ 1.75; 0 ≤ y < 0.55; 0.1 < z < 1; 0 ≤ a < 0.5; 0 ≤ b < 1; 0 ≤ c < 0.8; where M, N, and P are each at least one element selected from the following groups: Ti, Ta, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Zr, Y, Mo, Ru, Rh, and Sb; Li 1.25 No 0.25 Mr 0.50 O2;Li 1.3 No 0.3 Mr 0.40 O2;Li 1.3 No 0.3 Feb 0.40 O2;Li 1.3 No 0.43 Ni 0.27 O2;Li 1.3 No 0.43 Co 0.27 O2;Li 1.4 No 0.2 Mr 0.53 O2; Li x Ni 0.2 Mn 0.6 O y , where 0.00≤x≤1.52; 1.07≤y<2.4; Li 1.2 Ni 0.2 Mn 0.6 O2; LiNi x Co y Mn 1-x-y O2, where 0 ≤ x and y ≤ 0.5; LiNi x Ce z Co y Mn 1-x-y O2, where 0 ≤ x and y ≤ 0.5 and 0 ≤ z; phosphates LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2(PO4)3; Li2MPO4F, where M = Fe, Co, Ni or a mixture of these different elements; LiMPO4F, where M = V, Fe or T or a mixture of these different elements; LiMM'PO4, where M and M' are selected from Fe, Mn, Ni, Co, V and M and M' are different, where 0 < x < 1; Fe fluoride oxide 0.9 Co 0.1 OF; LiMSO4F, where M = Fe, Co, Ni, Mn, Zn, Mg; 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.

11. The method according to claim 1 , wherein the material P is selected from the group consisting of: Li4Ti5O 12 , Li4Ti 5-x M x O 12 , where M = V, Zr, Hf, Nb, Ta and 0 ≤ x ≤ 0.25; Niobium oxide and mixtures of niobium oxide with titanium, germanium, cerium or tungsten; Ti 1-x M 1 x Nb 2-y M 2 y O 7-z M 3 z or Li w Ti 1-x M 1 x Nb 2-y M 2 y O 7-z M 3 z ,in M 1 and M 2 are at least one element selected from the group consisting of 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 Same or different from each other, M 3 is at least one halogen, and where 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2, and z ≤ 0.3; TiNb2O 7-z M 3 z or Li w TiNb2O 7-z M 3 z , where M 3 is at least one halogen, and 0 < z ≤ 0.3; Ti 1-x Ge x Nb 2-y M 1 y The 7±z ,Li w Ti 1-x Ge x Nb 2-y M 1 y The 7±z ,Ti 1-x Yes x Nb 2-y M 1 y The 7±z ,Li w Ti 1-x Yes x Nb 2- y M 1 y The 7±z , among them M 1 is at least one element selected from the group consisting of 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; 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2 and z ≤ 0.3; Ti 1-x Ge x Nb 2-y M 1 y O 7-z M 2 z ,Li w Ti 1-x Ge x Nb 2-y M 1 y O 7-z M 2 z ,Ti 1-x Ce x Nb 2-y M 1 y O 7-z M 2 z ,Li w Ti 1- x Ce x Nb 2-y M 1 y O 7-z M 2 z， Wherein M 1 and M 2 are at least one element selected from the group consisting of 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, Ce, and Sn, M 1 and M 2 Same or different from each other, and where 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2 and z ≤ 0.3; TiO2; LiSiTON.

12. The method according to claim 11, wherein the material P is selected from the group consisting of: Nb2O 5±δ , Nb 18 W 16 O 93±δ , Nb 16 W5O 55±δ , where 0 ≤ x < 1 and 0 ≤ δ ≤ 2, LiNbO3; TiNb2O 7±δ , Li w TiNb2O7, where w≥0, Ti 1-x M 1 x Nb 2-y M 2 y O 7±δ or Li w Ti 1-x M 1 x Nb 2-y M 2 y O 7±δ , where M 1 and M 2 are at least one element selected from the group consisting of 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, respectively; M 1 and M 2 are the same as or different from each other, where 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2 and 0 ≤ δ ≤ 0.3; La x Ti 1-2x Nb 2+x O7, where 0 <x<0.5; M x Of 1-2x Nb 2+x SHE 7±δ where M is an element with an oxidation state of +III, and where 0 < x ≤ 0.20 and -0.3 ≤ δ ≤ 0.3; Ga 0.10 Ti 0.80 Nb 2.10 O7; Fe 0.10 Ti 0.80 Nb 2.10 O7; M x Of 2-2x Nb 10+x SHE 29±δ ; where M is an element with an oxidation degree of +III, and where 0 < x ≤ 0.40 and -0.3 ≤ δ ≤ 0.

3.

13. The method according to claim 1, wherein the inorganic material E comprises an electron-insulating material.

14. The method according to claim 13, wherein the inorganic material E comprises an electron-insulating material selected from: Al2O3, SiO2, ZrO2, and / or Materials selected from the group consisting of lithiated phosphates selected from: NaSICON type lithiated phosphates, Li3PO4; LiPO3; Li3Al 0.4 Sc 1.6 (PO4)3, called "LASP"; Li 1+x Zr 2-x Ca x (PO4)3, where 0 ≤ x ≤ 0.25; Li 1+2x Zr 2-x Ca x (PO4)3, where 0 ≤ x ≤ 0.25; LiZr2(PO4)3; Li 1+3x Zr2(P 1-x Si x O4)3, where 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 elements 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 and / or Y; Li 1+x M x (Ga) 2-x (PO4)3, where M = Al and / or Y 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 , where 0 ≤ x ≤ 0.8, 0 ≤ y ≤ 1.0, 0 ≤ z ≤ 0.6 and M = Al, Ga or Y or a mixture of two or three of these elements; Li 3+y (Sc 2-x M x )Q y P 3-y O 12 , where M = Al and / or Y, 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 elements 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 and / or Y, 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 M 3 x M 2-x P3O 12 , where 0 ≤ x ≤ 1, M 3 = Cr, V, Ca, B, Mg, Bi and / or Mo, M = Sc, Sn, Zr, Hf, Se or Si, or a mixture of these elements.

15. The method according to claim 1, wherein impregnating the assembly consisting of a porous electrode and a porous separator with an electrolyte selected from the group consisting of: an electrolyte consisting of at least one aprotic solvent and at least one lithium salt; an electrolyte consisting of at least one ionic liquid or poly(ionic liquid) and at least one lithium salt; a mixture of at least one aprotic solvent and at least one ionic liquid or poly(ionic liquid) and at least one lithium salt; an ion-conductive polymer produced by adding at least one lithium salt; and an ion-conductive polymer produced by adding a liquid electrolyte in a polymer phase or a mesoporous structure.

16. The method according to claim 15, wherein the polymer is selected from poly(ethylene oxide), poly(propylene oxide), polydimethylsiloxane, polyacrylonitrile, poly(methyl methacrylate), poly(vinyl chloride), poly(vinylidene fluoride), PVDF - hexafluoropropylene.

17. The method according to claim 1, wherein the method for manufacturing the assembly consisting of a porous electrode and a separator according to claim 8 is carried out to manufacture an assembly with the electrode as the positive electrode.

18. The method according to claim 1, wherein the method according to claim 9 is carried out to manufacture an assembly with the electrode as the negative electrode.

19. The method according to claim 17, wherein the assembly consisting of a porous electrode and a separator is impregnated with an electrolyte selected from the group consisting of: an electrolyte consisting of at least one aprotic solvent and at least one lithium salt; an electrolyte consisting of at least one ionic liquid or poly(ionic liquid) and at least one lithium salt; a mixture of an aprotic solvent and an ionic liquid or poly(ionic liquid) and a lithium salt; an ion-conductive polymer produced by adding at least one lithium salt; and an ion-conductive polymer produced by adding a liquid electrolyte or poly(ionic liquid) in a polymer phase or a mesoporous structure.

20. The method according to claim 19, wherein the polymer is selected from poly(ethylene oxide), poly(propylene oxide), polydimethylsiloxane, polyacrylonitrile, poly(methyl methacrylate), poly(vinyl chloride), poly(vinylidene fluoride), PVDF - hexafluoropropylene.

21. A lithium-ion battery obtainable by the method according to any one of claims 1 to 20.

22. An electrochemical device selected from the group consisting of a sodium-ion battery, a lithium-air battery, a fuel cell, and a photovoltaic cell, which is obtained by the manufacturing method according to any one of claims 1 to 20.