Method of making porous electrode and battery containing such electrode

Abstract

The present invention relates to a porous electrode useful in an electrical energy storage device or an electrical energy production device, such as a lithium ion battery. The porous electrode is a porous layer comprising at least one electrode active material P and an oxide electron conductor material.

Description

Technical Field

[0001] This invention relates to energy storage devices or energy production devices. More specifically, it relates to electrodes that can be used in energy storage or production devices, such as capacitors, photovoltaic cells, or ion-intercalated batteries, particularly lithium-ion, sodium-ion, and potassium-ion batteries. The invention is applicable to both negative and positive electrodes. It relates to porous electrodes that can be impregnated with an ion-conducting phase (e.g., a solid electrolyte or liquid electrolyte without a liquid phase).

[0002] The present invention also relates to a method for preparing such a porous electrode using an aggregate or cluster of nanoparticles of electrode material and at least one oxide electronic conductor material precursor, and the electrode obtained therefrom. The present invention further relates to a method for manufacturing an energy storage or generation device, and more particularly to a method for manufacturing a lithium-ion battery comprising at least one of these electrodes, and the battery obtained therefrom. Background Technology

[0003] Among various commercially available electrochemical storage technologies, lithium-ion batteries offer the best energy density. Electrodes with diverse structures and chemical compositions are available for manufacturing these batteries. Methods for producing lithium-ion batteries have appeared in numerous articles and patents; a review is provided in the 2002 book "Advances in lithium-Ion Batteries" (edited by W. van Schalkwijk and B. Scrosati), published by Kluever Academic / Plenum.

[0004] There is a growing need for very small rechargeable batteries that can be integrated onto electronic circuit boards; these circuits can be used in many fields, such as cards for secure transactions, electronic tags, implantable medical devices, and various micromechanical systems.

[0005] The demand for high-capacity rechargeable batteries is also growing, especially for powering and storing electrical energy in transportation equipment (electric bicycles, scooters, electric motorcycles, electric cars, electric commercial vehicles), such as storing electricity generated by intermittent power generation equipment (wind turbines, solar panels) or stabilizing power grids that are subject to highly fluctuating supply and demand.

[0006] The demand for medium-sized rechargeable batteries is also growing for various automated and portable devices, such as mobile phones, laptops, portable power tools, and intermittently used kitchen appliances.

[0007] In all these applications, the ability to quickly recharge the battery is a highly desirable feature. Similarly, these batteries must not be at risk of thermal runaway. Finally, it is desirable that they can operate over a wide temperature range.

[0008] According to existing technology, the electrodes of lithium-ion batteries can be produced using coating techniques, particularly by coating. These methods allow for the deposition of inks on the surface of a substrate, the inks consisting of active material particles in powder form; the average particle size of these powder particles is typically between 5 μm and 15 μm in diameter.

[0009] These deposition techniques, particularly coating, enable the production of layers with thicknesses ranging from approximately 20 µm to approximately 400 µm. The power and energy of the battery can be tuned by adjusting the layer thickness and porosity, the size of the active particles constituting the layer, and the presence of various components within the layer, such as binders or electronic conductor materials. For the production of microcells, it is desirable for each layer constituting the microcell to have a relatively thin thickness.

[0010] In addition to the issues related to ink formulations for obtaining high-performance electrodes at low production costs, it is important to remember that the ratio between the energy density and power density of an electrode can be adjusted as a function of the particle size of the active material, and indirectly based on the specific surface area and thickness of the electrode layer. J. Newman’s article ("Optimization of Porosity and Thickness of a Battery Electrode by Means of A Reaction-Zone Model", J. Electrochem. Soc., 142(1), pp. 97-101 (1995)) demonstrates the respective effects of electrode thickness and porosity on its state of discharge (power) and energy density.

[0011] Binder-free mesoporous electrode layers for lithium-ion batteries can be deposited via electrophoretic deposition; this is known from WO2019 / 215407 (I-TEN). They can be impregnated with liquid electrolytes, but their resistivity remains quite high.

[0012] To increase the low electronic conductivity of electrodes, especially when these electrodes are thick or made of electrode active materials with low electronic conductivity, a certain amount of electronically conductive material, such as carbon black, is typically added to the electrode active material particles. Ideally, the electronically conductive particles should be available at any point on the surface of the electrode active material particles so that they can be simultaneously inserted / extracted across the entire surface of the electrode active particles, thereby maximizing current density and minimizing stress and localized heating due to non-uniform electrical transport.

[0013] In practice, controlling the distribution of carbon black within the electrode is difficult. Furthermore, these problems become more prevalent with the increasing use of smaller and smaller active material particles. The non-uniform distribution of carbon black in the electrode leads to significantly higher polarization, resulting in increased series resistance in batteries containing such electrodes. The higher the current density, the more pronounced these imbalances in localized charge states become. These imbalances thus lead to losses in cycle performance, safety risks, and power limitations in the battery cell. The same applies when the electrode has non-uniform porosity, i.e., a non-uniform size distribution; this non-uniformity makes wetting of the electrode pores even more difficult.

[0014] In this context, to reduce the resistivity of the electrode, the applicant developed a mesoporous electrode comprising a mesoporous layer of at least one electrode active material, with a carbon coating on and within the pores of this mesoporous layer; this is known from WO2021 / 220174 (I-TEN). The presence of this carbon electronic conductor coating on the electrode allows for a reduction in its resistivity, but does not significantly improve its voltage, temperature, and electrochemical stability. Furthermore, producing a carbon electronic conductor coating on the electrode is costly and difficult to implement.

[0015] With the increasing demand for ultra-small rechargeable batteries, electrodes must meet increasingly stringent specifications. They must possess high chemical and electrochemical stability, robustness, and corrosion resistance to enable batteries containing them to exhibit high cycle performance, storage stability, temperature stability, and long-term reliability, combined with high energy density and high power density. This invention seeks to overcome at least some of the shortcomings of the prior art described above.

[0016] More precisely, the technical problem that this invention seeks to solve is to provide a method for manufacturing porous electrodes with high and uniform electronic conductivity and controllable pore density, which is simple, safe, fast, easy to implement and low in cost.

[0017] The present invention also aims to provide a safe porous electrode with high electronic conductivity, stable mechanical structure, good thermal stability (especially at high temperatures) and long service life, regardless of the electrode thickness.

[0018] Another object of the present invention is to provide an electrode for a battery that can operate at high temperatures without reliability issues and without the risk of fire.

[0019] Another object of the present invention is to provide a porous electrode that, in addition to the features described above, can be easily wetted and impregnated by ionic liquids or polymers.

[0020] Another object of the present invention is to provide a method for producing an energy storage device or energy production device (e.g., a capacitor, supercapacitor, hybrid supercapacitor, photovoltaic cell, photochemical cell or battery, particularly a lithium-ion battery, sodium-ion battery or even a potassium-ion battery) comprising a porous electrode according to the present invention.

[0021] Another object of the present invention is to provide an energy storage device or energy production device (e.g., a battery, particularly a lithium-ion battery and a micro battery, a capacitor, a supercapacitor, a hybrid supercapacitor, such as a lithium-ion hybrid supercapacitor, hereinafter referred to as LiC, a sodium-ion hybrid supercapacitor, hereinafter referred to as SIHC, and a potassium-ion hybrid supercapacitor, hereinafter referred to as PIHC) that can store high energy density, recover that energy at very high power density (especially in capacitors or supercapacitors), withstand high temperatures, have excellent cycle life, and increased safety. Summary of the Invention

[0022] In order to improve the performance of electrodes that can be used in energy storage devices or energy production devices, especially those that can be used in conventional lithium-ion batteries, particularly by reducing their resistivity while significantly improving their voltage, temperature and electrochemical stability, the inventors sought to find an alternative to the carbon electronic conductor coating proposed in application WO2021 / 220174 (I-TEN).

[0023] According to the invention, this problem is solved by an electrode for lithium-ion, sodium-ion, or potassium-ion batteries, which is entirely ceramic, porous, free of organic binders, and has a porosity of 25% to 60% by volume. The electrode according to the invention is a porous, preferably mesoporous layer comprising at least one electrode active material and an oxide electronic conductor material, with a porosity of 25% to 60% by volume. Advantageously, the electrode according to the invention includes a region of electrode active material P whose entire internal volume and surface are at least partially covered by a coating of oxide electronic conductor material; preferably, the electrode according to the invention includes a region of electrode active material P whose entire internal volume and surface are covered by a coating of oxide electronic conductor material.

[0024] This completely solid, porous, preferably mesoporous, organic-free layer is obtained from aggregates and / or aggregates of primary nanoparticles of at least one electrode active material and at least one oxide electronic conductor material precursor. The primary particles constituting these aggregates and / or aggregates are nanometer-sized or tens of nanometer-sized, and the aggregates and / or aggregates contain at least four primary particles.

[0025] The substrate may be a substrate capable of acting as an electron current collector in the first embodiment, or a temporary intermediate substrate in the second embodiment, which will be explained in more detail below.

[0026] The use of agglomerates with diameters of tens or even hundreds of nanometers, rather than non-agglomerated primary particles (each particle being approximately a few nanometers or tens of nanometers in size), allows for increased deposit thickness. However, the agglomerates must remain small to enable the formation of a continuous mesoporous film during the heat treatment of the layer. If the agglomerates are too large, this will hinder their sintering, and two distinct types of pores will be observed forming within the layer: pores between agglomerates and pores within the agglomerates.

[0027] After sintering, a porous, preferably mesoporous layer or plate is obtained, free of carbon black or organic binders, in which all primary nanoparticles are welded together (through necking or other known methods) to form a continuous mesoporous network characterized by a unimodal porosity. The resulting porous layer, preferably mesoporous, is completely solid and ceramic. During cycling, there is no longer any risk of loss of electrical contact between active material particles, which improves the cycle performance of the battery. Furthermore, after sintering, the porous, preferably mesoporous layer adheres perfectly to the metal substrate on which it has been deposited or transferred (in the case of initial deposition on an intermediate substrate).

[0028] High-temperature heat treatment sintersects the nanoparticles together, allowing for complete drying of the electrode and removal of any trace amounts of water, solvents, or other organic additives (stabilizers, binders) adsorbed on the surface of the active material particles. Prior to high-temperature heat treatment (sintering), a low-temperature heat treatment (debinding) can be performed to dry the placed or deposited electrode and remove any trace amounts of water, solvents, or other organic additives (stabilizers, binders) adsorbed on the surface of the active material particles; this debinding can be carried out in an oxidizing atmosphere.

[0029] The porosity of the final electrode can be adjusted according to the sintering time and temperature. Depending on the energy density requirements, the porosity can be adjusted within the range of 25% to 60%.

[0030] In all cases, the power density of the electrode thus obtained remains extremely high due to its porosity, preferably due to its mesoporous nature. Furthermore, regardless of the size of the mesopores in the active material (the concept of nanoparticles after sintering is known to no longer apply to materials with three-dimensional structures containing channels and mesoporous networks), the dynamic balance of the battery remains perfect, which helps to maximize the battery's power density and lifespan.

[0031] The electrode according to the invention has a high specific surface area, which reduces the ionic resistance of the electrode. However, in order for the electrode to provide maximum power, it must also have very good electronic conductivity to prevent ohmic losses in the battery. The greater the electrode thickness, the more critical it is to improve the electronic conductivity of the cell. Furthermore, this electronic conductivity must be completely uniform throughout the electrode to prevent localized areas of high resistance, which could lead to hot spots during power operation of the battery.

[0032] According to an essential feature of the invention, the electrode according to the invention comprises at least one electrode active material and an oxide electronic conductor material, preferably comprising a region of electrode active material P in which the entire internal volume of the electrode and the surface are at least partially covered with a coating of oxide electronic conductor material, and preferably comprising a region of electrode active material P in which the entire internal volume of the electrode and the surface are covered with a coating of oxide electronic conductor material in a perfectly distributed manner.

[0033] The coating of the oxide electronic conductor material according to the invention is advantageously SnO2, aluminum-doped ZnO (ZnO:Al, preferably having a Zn:Al ratio of 1:0.015 to 1:0.05), MoO3, SrMoO3, In2O3, Ga2O3 or indium tin oxide.

[0034] The thickness of the oxide electronic conductor material coating throughout the entire internal volume of the electrode is advantageously less than 10 nm, preferably less than 7 nm, more preferably less than 5 nm, more preferably 5 nm to 3 nm, and even more preferably less than 3 nm. This oxide electronic conductor material can be produced from at least one precursor of the oxide electronic conductor material, particularly from at least one liquid precursor of the oxide electronic conductor material.

[0035] This thickness can be measured using any suitable technique, particularly by transmission electron microscopy.

[0036] More specifically, as described above, the method according to the invention must include the step of forming a layer of agglomerated nanoparticles of electrode material (active material) and at least one oxide electronic conductor material precursor, resulting in the nanoparticles naturally "welding" together, producing a porous rigid three-dimensional structure after consolidation such as annealing, without the need for organic binders; such porous layer, preferably mesoporous layer, is well-suited for surface treatment by gas or liquid means, or by immersion into the depth of the open porous structure of the layer.

[0037] The first object of the present invention is a method for producing porous electrodes, particularly for use in energy storage devices or energy generation devices (e.g., batteries), wherein the electrode is a porous layer deposited on a substrate comprising at least one electrode active material P and an oxide electronic conductor material, the electrode being binder-free, having a porosity of 25 vol% to 60 vol%, preferably 25 vol% to 50 vol%, and pores with an average diameter of less than 100 nm, and the production method is characterized by comprising: (a) A colloidal suspension or paste comprising a substrate, at least one oxide electronic conductor material precursor, and primary nanoparticles comprising at least one electrode active material P, wherein the average primary diameter D of the primary nanoparticles is D. 50 The average diameter D of the aggregates or agglomerates is 2 nm to 400 nm, preferably 2 nm to 100 nm, more preferably 2 nm to 60 nm. 50 The nm range is 50 nm to 900 nm, preferably 100 nm to 800 nm. It should be understood that the substrate can be a substrate capable of acting as an electron current collector, or an intermediate substrate. (b) The one or more oxide electronic conductor material precursors provided in step (a) are mixed with the colloidal suspension or paste of an aggregate or agglomerate containing at least one electrode active material P to form a mixture. (c) A mixture layer obtained at the end of step (b) is formed by a method selected from the group consisting of: electrophoresis, additive manufacturing, printing, preferably inkjet printing or flexographic printing, coating, preferably blade coating, roller coating, curtain coating, dip coating or slot extrusion coating.

[0038] (d) Dry the layer obtained in step (c) to obtain a dried layer, wherein, if necessary, the dried layer is separated from its intermediate substrate after drying step (d). (e) Converting one or more oxide electronic conductor material precursors into oxide electronic conductor materials, such that the dried layer comprises the oxide electronic conductor material. (f) The layer is cured by heat treatment and / or mechanical treatment, preferably by sintering, to obtain a porous electrode, preferably a mesoporous electrode. It should be understood that steps (e) and (f) can be performed in the same heat treatment process.

[0039] The method according to the invention may include heat-treating the dried layer in step (e), step (f), or between steps (e) and (f), preferably in an oxidizing atmosphere.

[0040] Advantageously, after step (f), the pores of the porous electrode are impregnated with an electrolyte. Depending on the intended battery type, the electrolyte may include a lithium salt, potassium salt, or sodium salt. The electrolyte is preferably a phase carrying lithium ions, sodium ions, or potassium ions, selected from the group consisting of: ○ An electrolyte consisting of at least one aprotic solvent and at least one lithium salt, sodium salt, or potassium salt; ○ An electrolyte consisting of at least one ionic liquid and at least one lithium salt, sodium salt, or potassium salt; ○ A mixture of at least one aprotic solvent, at least one ionic liquid, and at least one lithium, sodium, or potassium salt; ○ Ionic liquid polymers; ○ Polymer ionic conductors made by adding at least one lithium salt, sodium salt, or potassium salt; and ○ By adding a liquid electrolyte to the polymer phase or porous structure of the porous electrode, or by using a polymer ion conductor made of an ion conductor polymer, The ion-conducting polymer is preferably selected from polyethylene oxide (PEO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(propylene carbonate) (PPC), poly(carbonate) (PEC), poly(ethylene carbonate) (PVC), polyvinylidene fluoride (PVDF), polypropylene glycol (PPG), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polydimethylsiloxane (PDMS), poly(ε-caprolactone) (PCL), and poly(trimethylene carbonate) (PTMC).

[0041] The lithium-ion-carrying phase can comprise a mixture of various ionic liquids. Advantageously, the ionic liquid can be 1-ethyl-3-methylimidazolium (also known as EMI+) and / or n-propyl-n-methylpyrrolidineium (also known as PYR). 13 + ) and / or n-butyl-n-methylpyrrolidone (also known as PYR) 14 + A cation of type ) with bis(trifluoromethanesulfonyl)imide (TFSI) - ) and / or bis(fluorosulfonyl)imide (FSI) -The electrolyte is formed by the binding of anions of the type 1, 2, 3, 4, 5, 6 ...

[0042] In step (c), a layer may be formed on one or both sides of the substrate.

[0043] Advantageously, when the substrate is an intermediate substrate, after drying the layers, especially after consolidation, the layers of the intermediate substrate are separated in step (d) to form a porous plate.

[0044] Advantageously, when the substrate is an intermediate substrate, after step (f), an electronically conductive sheet is provided, which is covered with a conductive adhesive film on at least one side, and respectively on two sides thereof. Then, at least one porous plate is bonded to one side of the electronically conductive sheet, preferably on each side, to obtain a porous, preferably mesoporous plate or layer on the substrate capable of acting as an electron current collector. In this application, the terms "porous layer" and "porous plate" are interchangeable.

[0045] Advantageously, step (b) is carried out by contacting a colloidal suspension or paste of aggregates or clusters of primary nanoparticles containing at least one electrode active material P provided in step (a) with a liquid phase containing at least one precursor of the oxide electronic conductor material, and wherein the conversion of the one or more oxide electronic conductor material precursors to the oxide electronic conductor material during step (e) is carried out by heat treatment such as calcination, preferably in air or an oxidizing atmosphere.

[0046] Advantageously, the one or more oxide electronic conductor material precursors are selected from organic salts containing one or more metal elements that are capable of forming oxide electronic conductors after heat treatment such as calcination, and the conversion to electronic conductor material is carried out by heat treatment such as calcination, preferably in air or an oxidizing atmosphere.

[0047] These organic salts are preferably selected from: - An alkoxide of at least one metallic element that can form an oxide electronic conductor after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination. - A nitrate of at least one metallic element that can form an oxide electronic conductor after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination. - Oxalates of at least one metallic element capable of forming oxide electronic conductors after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination. - Acetates of at least one metallic element that are capable of forming oxide electronic conductors after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination. And / or preferably, the metallic element is selected from tin, zinc, indium, gallium, molybdenum, or a mixture of two, three, four, or five of these elements.

[0048] Metallic elements may include at least one doping element.

[0049] Advantageously, the porous layer obtained at the end of step (f) has a density of 10 m. 2 / g to 500m 2 A specific surface area of ​​ / g and / or a thickness of 2µm to 400µm, preferably 2µm to 300µm, more preferably 3µm to 200µm.

[0050] Advantageously, when the substrate is one that can be used as an electron current collector, the porous layer obtained at the end of step (f) has a density of 10 μm. 2 / g to 500m 2 Specific surface area per g and / or thickness from 2µm to 20µm.

[0051] Advantageously, when the substrate is an intermediate substrate, the porous layer obtained at the end of step (f) has a density of 10 μm. 2 / g to 500m 2 A specific surface area of ​​ / g and / or a thickness of 25µm to 500µm, preferably 50µm to 400µm.

[0052] Advantageously, when the colloidal suspension or paste provided in step (a) contains organic additives, such as ligands, stabilizers, binders or residual organic solvents, the dried layer or the porous plate obtained at the end of step (d) is heat-treated, preferably in an oxidizing atmosphere. It should be understood that this heat treatment and steps (e) and / or (f) can be performed in the same heat treatment step.

[0053] Advantageously, the electrode active material P is selected from the group (A) formed below: ○ Oxides LiMn2O4, Li 1+x Mn 2-x O4, where 0 <x< 0.15,LiCoO2、LiNiO2、LiMn 1.5 Ni 0.5 O4, LiMn1.5 Ni 0.5-x X x O4, where X is selected from Al, Fe, Cr, Co, Rh, Nd, other rare earth elements such as Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and where 0 < x < 0.1, LiMn 2-x M x O4, where M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg, or a mixture of these elements, and where 0 < x < 0.4, LiFeO2, LiMn 1 / 3Ni 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, where 0.6 ≤ y ≤ 0.85; 0 ≤ x + y ≤ 2; and 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 the following: 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, and 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; and where M, N, and P are each at least one element selected from the group consisting of: Ti, Ta, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Zr, Y, Mo, Ru, Rh, Ce, and Sb; ○ 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; ○ 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, T or a mixture of these different elements; phosphates of the formula Li MM’PO4, where M and M’ (M ≠ M’) are selected from Fe, Mn, Ni, Co, V, for example LiFe x Co 1-x PO4, and where 0 < x < 1; ○ Fe0.9 Co 0.1 OF; FeF3; LiMSO4F, where M = Fe, Co, Ni, Mn, Zn, Mg; ○ 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, Li x V2O5, where 0 < x ≤ 2, Li x V3O8, where 0 < x ≤ 1.7, Li x TiS2, where 0 < x ≤ 1, lithium titanium oxysulfide Li x TiO y S z , where z = 2 - y, 0.3 ≤ y ≤ 1 and 0 < x ≤ 1, Li x WO y S z , where z = 2 - y, 0.3 ≤ y ≤ 1 and 0 < x ≤ 1, Li x CuS, where 0 < x ≤ 1, Li x CuS2, where 0 < x ≤ 1; Or selected from the group (B) formed by: - Transition metal oxides: ○ Na x MO 2+z , where M is selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ Na x M u / 2 M’ v / 2 O 2+z where u + v = 2 and M, M’ are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ Na x M u / 3 M’ v / 3 M’’ w / 3 O 2+zwhere \(u + v+w = 3\) and \(M\), \(M'\), \(M''\) are selected from \(Mg\), \(Ca\), \(Li\), \(Mn\), \(Ni\), \(Co\), \(Cr\), \(Sc\), \(Te\), where \(z\leq0.3\) and \(0\lt x\leq1\), preferably \(0\lt x\lt0.44\) or \(0.44\leq x\leq0.67\) or \(0.67\lt x\leq1\); ○ Na x Mn y Ni z Fe 0.1 Mg 0.1 O2, where \(0.67\leq x\leq1.0\); \(0.5\leq y\leq0.7\) and \(0.1\leq z\leq0.3\); - Prussian blue and / or Prussian blue analogs, abbreviated as PBA: ○ Na x M 1 [M 2 ’(CN)6] y .nH2O, M 1 is a transition metal or a transition metal alloy, M 2 ’ is a transition metal, the transition metal and the transition metal alloy are selected from Fe, Ni, Co and Mn, where \(0\leq x\leq2\); \(y\leq1\) and \(0\leq n\leq12\); - Polyanion compounds: ○ Na x M2(XO4)3, where \(0\lt x\leq4\), \(M = V\), \(Fe\), \(Cr\), \(Mn\), \(Co\), \(Ni\) or \(Sc\) and \(X = P\), \(S\), \(As\), \(Si\), \(Mo\) or \(W\), such as Na3V2(PO4)3; ○ Na x M3(XO4)2(X2O7), where \(0\lt x\leq4\), \(M = V\), \(Fe\), \(Cr\), \(Mn\), \(Co\), \(Ni\) or \(Sc\) and \(X = P\), \(S\), \(As\), \(Si\), \(Mo\) or \(W\); ○ Na x M(X2O7), where \(0\lt x\leq4\), \(M = V\), \(Fe\), \(Cr\), \(Mn\), \(Co\), \(Ni\) or \(Sc\) and \(X = P\), \(S\), \(As\), \(Si\), \(Mo\) or \(W\); ○ Na x M2(XO4)2F3, where \(0\lt x\leq4\), \(M = V\), \(Fe\), \(Cr\), \(Mn\), \(Co\), \(Ni\) or \(Sc\) and \(X = P\), \(S\), \(As\), \(Si\), \(Mo\) or \(W\); ○ Na x M2(XO4)2F 3-y O y , where \(0\lt x\leq4\), \(M = V\), \(Fe\), \(Cr\), \(Mn\), \(Co\), \(Ni\) or \(Sc\) and \(0.07\leq y\leq0.12\) and \(X = P\), \(S\), \(As\), \(Si\), \(Mo\) or \(W\); ○ Na xM2O2(XO4)2F, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ Na x MXO4, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; or a group (C) selected from the following: - Transition metal oxides: ○ K x MO 2+z , where M is selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ K x M u / 2 M’ v / 2 O 2+z , where u + v = 2 and M, M’ are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ K x M u / 3 M’ v / 3 M’’ w / 3 O 2+z where u + v + w = 3 and M, M’, M’’ are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ K x Mn y Ni z Fe 0.1 Mg 0.1 O2, where 0.67 ≤ x ≤ 1.0; 0.5 ≤ y ≤ 0.7 and 0.1 ≤ z ≤ 0.3; - Prussian blue and / or Prussian blue analogs, abbreviated as PBA: ○ K x M 1 [M 2 ’(CN)6] y .nH2O, M 1 is a transition metal or a transition metal alloy, M 2 ’ is a transition metal, the transition metal and the transition metal alloy are selected from Fe, Ni, Co and Mn, where 0 ≤ x ≤ 2; y ≤ 1 and 0 ≤ n ≤ 12; - Poly - anion compounds: ○ K x M2(XO4)3, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W, such as Na3V2(PO4)3; ○ K x M3(XO4)2(X2O7), where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ K x M(X2O7), where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ K x M2(XO4)2F3, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ K x M2(XO4)2F 3-y O y , where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and 0.07 ≤ y ≤ 0.12 and X = P, S, As, Si, Mo or W; ○ K x M2O2(XO4)2F, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ K x MXO4, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W.

[0054] Advantageously, the above - mentioned electrode active material P is used to manufacture a cathode.

[0055] Advantageously, the electrode active material P is selected from the group (D) formed by: ○ Li4Ti5O 12 、Li4Ti 5-x M x O 12 , where M = V, Zr, Hf, Nb, Ta and 0 ≤ x ≤ 0.25; ○ Niobium oxides and oxides of niobium mixed with titanium, germanium, cerium or tungsten, and preferably selected from the group consisting of: ○ Nb2O 5±δ 、Nb 12 WO 33±δ, Nb 14 W3O 44±δ , Nb 18 W 16 O 93±δ , Nb 16 W5O 55±δ , where 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 each 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 can be the same as or different from each other, and where 0≤w ≤ 5 and 0 ≤ x ≤ 1 and 0 ≤ y ≤ 2 and 0 ≤ δ ≤ 0.3; ○ La x Ti 1-2x Nb 2+x O7, where 0<x<0.5; ○ M x Ti 1-2x Nb 2+x O 7±δ , ○ where M is an element with an oxidation value of +III, more particularly, M is at least one element selected from the group consisting of Fe, Ga, Mo, Al, B 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 Ti 2-2xNb 10+x O 29±δ , ○ wherein M is an element with an oxidation state of +III, and more particularly, M is at least one element selected from the group consisting of Fe, Ga, Mo, Al, B and wherein 0 < x ≤ 0.40 and -0.3 ≤ δ ≤ 0.3; ○ 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 wherein ○ M 1 and M 2 are each 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 can be the same or different from each other, ○ M 3 is at least one halogen, ○ and wherein 0 ≤ w ≤ 5 and 0 ≤ x ≤ 1 and 0 ≤ y ≤ 2 and z ≤ 0.3; ○ TiNb2O 7-z M 3 z or Li w TiNb2O 7-z M 3 z wherein M 3 is at least one halogen, preferably selected from F, Cl, Br, I or a mixture thereof, wherein 0 < z ≤ 0.3 and 0 < w ≤ 0.5; ○ Ti 1-x Ge x Nb 2-y M 1 y O 7±z 、Liw Ti 1-x Ge x Nb 2-y M 1 y O 7±z Ti 1-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 ○ M 1 For 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 and 0 ≤ x ≤ 1 and 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 ,in ○ M1 and M 2 each 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, Ce, and Sn, ○ M 1 and M 2 may be the same as or different from each other, ○ and wherein 0 ≤ w ≤ 5 and 0 ≤ x ≤ 1 and 0 ≤ y ≤ 2 and z ≤ 0.3; ○ TiO2; TiO x N y , where x < 2 and 0 < y < 0.2; ○ LiSiTON, tin- and silicon-based oxynitrides, more particularly the formulation SiSn 0.87 O 1.20 N 1.72 and its lithiated forms; ○ nitrides and MO x N y type oxynitrides, where M is at least one element selected from: Ge, Si, Sn, Zn, Co, Ni, Cu, Fe or a mixture of one or more of these elements, where x ≥ 0 and y ≥ 0.3; ○ Li 3-x M x N, where M is at least one element selected from: Cu, Ni, Co or a mixture of one or more of these elements and 0 ≤ x ≤ 1; ○ Li 3-x M x N, where M is cobalt (Co) and 0 ≤ x ≤ 0.5; Li 3-x M x N, where M is nickel (Ni) and 0 ≤ x ≤ 0.6; Li 3-x M x N, where M is copper (Cu) and 0 ≤ x ≤ 0.3; ○ lithiated iron phosphate having the typical molecular formula LiFePO4; ○ having the typical molecular formula Si a Sn b O y N z of mixed silicon tin oxynitrides, where a > 0, b > 0, a + b ≤ 2, 0 < y ≤ 4, 0 < z ≤ 3, also known as SiTON, and more particularly SiSn 0.87 O 1.2 N 1.72; and Si, which has a typical molecular formula a Sn b C c O y N z oxynitrides and carbides, where a>0, b>0, a+b≤2, 0 <c<10、0<y<24、0<z<17; ○ Si x N y Type nitrides, particularly where x = 3 and y = 4; Sn x N y In particular, where x = 3 and y = 4, Zn x N y In particular, where x = 3 and y = 2; Li 3-x M x N, where for M=Co, 0 ≤ x ≤ 0.5, for M=Ni, 0 ≤ x ≤ 0.6, and for M=Cu, 0 ≤ x ≤ 0.3; Si 3-x M x N4, where M = Co or Fe and 0 ≤ x ≤ 0.3, ○Oxides SnO2, SnO, Li2SnO3, SnSiO3, Li x SiO y Where x>=0 and 2>y>0, Li4Ti5O 12 TiNb2O7, Co3O4, SnB 0.6 P 0.4 O 2.9 and TiO2, ○ Si, Sn, SiO2, SnO2, SiN, SnN and their mixtures ○ A composite oxide TiNb2O7 containing 0% to 10% carbon, preferably selected from graphene and carbon nanotubes; Or choose from the following groups (E): - Alloys based on Si, Ge, Sn, Sb, Bi, or P, and alloys of these different compounds. - Maicoene, a class of two-dimensional materials with a stoichiometry of M n+1 X n T x Type, wherein M is a transition metal, preferably selected from Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, W, and X is selected from C and / or N, and the surface terminator T is selected from F, Cl, I, Br, O, S, Se, Te, OH, NH2, 1≤n≤4 -Convert anode materials, for example ○G2Ti3O7, G4Ti5O12、 GTi2(PO4)3 type oxide, where G is Na or K. ○ The oxides, sulfides, selenides, and phosphides of the following elements and their alloys: Si, Ge, Sn, Sb, Bi.

[0056] Advantageously, the aforementioned electrode active material P is used to manufacture an anode.

[0057] Another object of the present invention is a porous electrode, particularly a porous electrode for an energy storage device or an energy production device, characterized in that it comprises at least one electrode active material P and an oxide electronic conductor material, which is free of binder and has a porosity of 25 vol% to 60 vol%, preferably 25 vol% to 50 vol%.

[0058] Another object of the present invention is a porous electrode that can be obtained by the method according to the invention. This porous electrode comprises at least one electrode active material P and an oxide electronic conductor material, which is binder-free and has a porosity of 25 vol% to 60 vol%, preferably 25 vol% to 50 vol%.

[0059] Another object of the present invention is a method for producing an energy storage device or an energy production device, a method for producing a porous electrode according to the present invention, or a method for using a porous electrode according to the present invention, wherein the device is preferably selected from the group consisting of: capacitors, supercapacitors, hybrid supercapacitors (such as lithium-ion hybrid supercapacitors, sodium-ion hybrid supercapacitors, potassium-ion hybrid supercapacitors), photovoltaic cells, photoelectrochemical cells, and batteries such as lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries. Another object of the present invention is a method for producing an energy storage device or an energy production device, particularly a method for producing lithium-ion, sodium-ion, or potassium-ion batteries, and a method for producing a porous electrode according to the present invention, wherein the device is, for example, a battery, capacitor, supercapacitor, hybrid supercapacitor (such as lithium-ion hybrid supercapacitors, sodium-ion hybrid supercapacitors, potassium-ion hybrid supercapacitors), photoelectrochemical cells, and photovoltaic cells.

[0060] Advantageously, when the energy storage device or energy production device is a lithium-ion hybrid supercapacitor or a lithium-ion battery, the cathode production method uses the electrode active material P selected in group (A), or the anode production method uses the electrode active material P selected in group (D).

[0061] Advantageously, when the energy storage device or energy production device is a lithium-ion hybrid supercapacitor or a lithium-ion battery, the cathode production method uses the electrode active material P selected in group (B), or the anode production method uses the electrode active material P selected in group (E) (where G is Na if necessary).

[0062] Advantageously, when the energy storage device or energy production device is a potassium-ion hybrid supercapacitor or a potassium-ion battery, the cathode production method uses an electrode active material P selected in group (C), or the anode production method uses an electrode active material P selected in group (E) (where G is Na if necessary).

[0063] Advantageously, in the method of preparing a lithium-ion battery, the method of preparing a porous electrode is carried out to prepare a cathode using an electrode active material P selected from group (A), or the method of preparing a porous electrode is carried out to prepare an anode using an electrode active material P selected from group (D).

[0064] In particular, this method is well-suited for battery production, and typically, batteries according to the invention can be designed and sized as surface mount assemblies (surface mount technology is often abbreviated as "SMT") to be compatible with methods for manufacturing microelectronics, especially with robotic methods used to fill electronic circuit boards, referred to in the term "pick-and-place".

[0065] Advantageously, the porous electrode is impregnated with an electrolyte, preferably with a phase carrying lithium ions, sodium ions, or potassium ions, wherein the electrolyte is selected from the group consisting of: ○ An electrolyte consisting of at least one aprotic solvent and at least one lithium salt, sodium salt, or potassium salt; ○ An electrolyte consisting of at least one ionic liquid and at least one lithium salt, sodium salt, or potassium salt; ○ A mixture of at least one aprotic solvent, at least one ionic liquid, and at least one lithium, sodium, or potassium salt; ○ Ionic liquid polymers; ○ Polymer ionic conductors made by adding at least one lithium salt, sodium salt, or potassium salt; and ○ Polymer ion conductors are made by adding liquid electrolytes to polymer phases or porous structures, or by using polymers with ion-conducting polymers. The ion-conducting polymer is preferably selected from polyethylene oxide (PEO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(propylene carbonate) (PPC), poly(carbonate) (PEC), poly(ethylene carbonate) (PVC), polyvinylidene fluoride (PVDF), polypropylene glycol (PPG), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polydimethylsiloxane (PDMS), poly(ε-caprolactone) (PCL), and poly(trimethylene carbonate) (PTMC).

[0066] Another object of the present invention is an energy storage device or energy production device that can be obtained by the method according to the present invention, preferably a battery that can be obtained by the method according to the present invention, preferably a lithium-ion, sodium-ion or potassium-ion battery.

[0067] Advantageously, the energy storage device or energy production device according to the invention is a capacitor, a supercapacitor, a hybrid supercapacitor (such as a lithium-ion hybrid supercapacitor, a sodium-ion hybrid supercapacitor, or a potassium-ion hybrid supercapacitor), a photovoltaic cell, a photoelectrochemical cell, or a battery such as a lithium-ion battery, a sodium-ion battery, or a potassium-ion battery.

[0068] Advantageously, when the energy storage device or energy production device is a lithium-ion hybrid supercapacitor or a lithium-ion battery, the electrode active material P is selected in group (A) for cathode active material and / or in group (D) for anode active material.

[0069] Advantageously, when the energy storage device or energy production device is a sodium-ion hybrid supercapacitor or sodium-ion battery, the electrode active material P is selected in group (B) for the cathode active material and / or in group (E) for the anode active material (where applicable, G is Na).

[0070] Advantageously, when the energy storage device or energy production device is a potassium-ion hybrid supercapacitor or potassium-ion battery, the electrode active material P is selected in group (C) for cathode active material and / or in group (E) for anode active material (where applicable, G is K).

[0071] The method according to the invention is particularly suitable for producing porous electrodes with a thickness greater than 1µm, or even greater than 3µm, while ensuring low series resistance of the battery.

[0072] Another object of the present invention is an energy storage device or energy production device, such as a battery, container, supercapacitor, photovoltaic cell or photochemical cell, comprising a porous electrode according to the present invention or a porous electrode that can be obtained by the method according to the present invention. Detailed Implementation

[0073] 1. Definition This invention relates to a porous electrode whose accessible surfaces, namely the outer surface of the electrode and its accessible internal pores, are covered with an oxide electronic conductor material. The term "oxide electronic conductor" includes oxide electronic conductors and oxide electronic semiconductors.

[0074] Within the scope of this document, particle size is defined by its largest dimension. The term "nanoparticle" shall refer to any particle or object of the nanoscale, having at least one dimension less than or equal to 400 nm.

[0075] The term "ionic liquid" refers to any liquid salt capable of transmitting electricity, distinguished from molten salts by its melting temperature being below 100°C. Some of these salts remain liquid at ambient temperature and do not solidify even at very low temperatures. Such salts are called "ambient temperature ionic liquids."

[0076] The term "electrolyte" refers to any ionicly conductive material that exhibits conductivity due to the presence of mobile ions; it can be a solid without a liquid phase or a liquid. These ions are preferably Li+, Na+, or K+. Liquid electrolytes can be in gel form. To electrically isolate the electrodes, the electrolyte is electrically insulating.

[0077] The term "mesoporous material" refers to any solid having pores within its structure that are called "mesoporous pores," having an intermediate size between micropores (width less than 2 nm) and macropores (width greater than 50 nm), i.e., a size of 2 nm to 50 nm. This term corresponds to the terminology adopted by IUPAC (International Union of Pure and Applied Chemistry), which is a reference for those skilled in the art. Therefore, the term "nanopore" is not used herein, even though the mesopores defined above have nanoscale dimensions within the meaning of the definition of nanoparticles; it is understood that pores smaller than the size of mesopores are referred to as "micropores" by those skilled in the art.

[0078] The article "Texture des materials pulverulents ou poreux" (Texture of powdery or porous materials) by F. Rouquerol et al., published in "Techniques de l'Ingénieur" (Techniques for the Engineer), treaties, Analyse et Caractérisation (Analysis and Characterisation), on page 1050, introduces the concept of porosity (and the terminology just explained above); the article also describes techniques for characterizing porosity, particularly the BET method.

[0079] In the context of this invention, the term "porous layer" refers to a layer having a plurality of pores. The term "mesoporous layer" refers to a layer having mesopores. In these layers, pores and mesopores make a significant contribution to the total porous volume; this is demonstrated by the expression "porous / mesoporous layer with a porosity greater than X volume %" used in this specification.

[0080] According to the IUPAC definition, the term "aggregate" refers to a weakly bonded collection of primary particles. In this case, these primary particles, preferably nanoparticles, are particles with a diameter that can be measured by transmission electron microscopy. Using techniques known to those skilled in the art, aggregates of primary nanoparticles can typically be broken down (i.e., reduced to primary nanoparticles) in a suspension in a liquid phase under the influence of ultrasound.

[0081] According to the IUPAC definition, the term "aggregate" refers to a strongly bound aggregate of primary particles or aggregates.

[0082] 2. Preparation of Nanoparticle Suspensions The porous electrode according to the present invention is formed from a colloidal suspension or paste of clusters and / or aggregates of nanoparticles.

[0083] In a more preferred embodiment of the invention, nanoparticles having their primary size are directly prepared by precipitation, Pechini synthesis, spray pyrolysis, hydrothermal synthesis, or solvothermal synthesis. Hydrothermal synthesis or solvothermal synthesis can be used to obtain nanoparticles, preferably nanoparticles with a very narrow size distribution, referred to as “monodisperse nanoparticles.” The size of these non-aggregated or non-clustered nanopowders / nanoparticles is referred to as the primary size. It is typically between 2 nm and 400 nm, preferably between 2 nm and 100 nm, more preferably between 2 nm and 60 nm, advantageously between 10 nm and 50 nm, preferably between 10 nm and 30 nm; in subsequent method steps, this promotes the formation of an interconnected mesoporous network of electron and ion conduction through a “neck-in” phenomenon.

[0084] Additives, such as binders, can also be added to suspensions of nanoparticles (clusters and / or aggregates of nanoparticles, which are known to also be in the form of nanoparticles) to promote the formation of deposits or green sheets, particularly thick deposits without cracks.

[0085] By any suitable means, a layer of at least one oxide electronic conductor material precursor is formed on these preferred monodisperse aggregates and / or clusters of primary nanoparticles of at least one electrode active material P.

[0086] 3. A mixture comprising a colloidal suspension or paste of at least one oxide electronic conductor material precursor and aggregates and / or agglomerates of primary particles comprising at least one electrode active material P. A layer of at least one oxide electronic conductor material precursor is formed on the aggregates and / or agglomerates of the primary particles of at least one electrode active material P.

[0087] Advantageously, oxide electronic conductor material layers can be obtained in various ways and by any suitable means, particularly by contacting a colloidal suspension or paste containing aggregates or clusters of primary nanoparticles of at least one electrode active material P with a liquid phase containing at least one oxide electronic conductor material precursor, and subsequently converting the one or more electronic conductor material precursors into electronic conductor materials.

[0088] More generally, the techniques described herein for producing coatings of at least one oxide electronic conductor material precursor are used to cover only the accessible surface of an aggregate or cluster of primary nanoparticles of at least one electrode active material P.

[0089] The formation of a layer of at least one oxide electronic conductor material precursor on aggregates or agglomerates in the form of suspensions or pastes is advantageously carried out in the presence of a complexing agent such as polyvinylpyrrolidone (PVP) to promote the complexation of one or more precursors on the surface of the aggregates / agglomerates.

[0090] This method is simple, rapid, and easy to implement. Advantageously, one or more precursors of the electronically conductive material are selected from organic salts containing one or more metal elements, which are capable of forming oxide electronic conductors after heat treatment such as calcination (preferably in air or an oxidizing atmosphere). The oxide electronic conductor may optionally contain at least one doping element. These metal elements, preferably metal cations, may advantageously be selected from tin, zinc, indium, gallium, molybdenum, or mixtures of two, three, or four of these elements. The organic salt is preferably selected from: - An alkoxide of at least one metallic element that can form an oxide electronic conductor after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination. - A nitrate of at least one metallic element that can form an oxide electronic conductor after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination. - Oxalates of at least one metallic element capable of forming oxide electronic conductors after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination. - Acetates of at least one metallic element that can form oxide electronic conductors after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination.

[0091] To obtain an electronic conductor material (preferably an oxide electronic conductor material) layer formed of alkoxide, nitrate, oxalate or acetate on an aggregate or cluster of primary nanoparticles of at least one electrode active material P, a colloidal suspension or paste containing the aggregate or cluster of said nanoparticles can be contacted with a solution rich in the desired electronic conductor material precursor.

[0092] It is a mixture of a colloidal suspension or paste comprising aggregates or agglomerates of primary nanoparticles containing electrode active material P and at least one oxide electronic conductor material precursor, which is then used to produce a porous dried layer and an electrode according to the invention. This mixture of the colloidal suspension or paste comprising aggregates or agglomerates of primary nanoparticles containing electrode active material P and at least one oxide electronic conductor material precursor is hereinafter referred to as "the mixture according to the invention". Advantageously, the mixture according to the invention is in the form of a colloidal suspension or paste (ink).

[0093] 4. Fabrication of porous layers The method for producing electrodes according to the invention includes applying a mixture of a colloidal suspension or paste comprising an aggregate or agglomerate of one or more oxide electronic conductor material precursors and at least one primary nanoparticle of electrode active material P onto a substrate to form a layer, and then drying the layer to obtain a porous layer. To increase the thickness of the porous layer, the sequence of applying the mixture to the substrate to form the layer and drying may be repeated multiple times. The final thickness of the porous layer is advantageously less than or equal to 5 mm, preferably from about 1 µm to about 500 µm. The thickness of the porous layer is advantageously less than 500 μm, preferably from about 2 μm to about 400 μm, more preferably from 2 μm to 300 μm, and even more preferably from 3 μm to 200 μm. Typically, the mixture according to the invention is deposited on a substrate in the form of a colloidal suspension or paste by any suitable technique, particularly by methods such as electrophoresis, extrusion, additive manufacturing (or robotic casting), inkjet printing, spraying, flexographic printing, coating methods, preferably using a doctor blade (referred to as "doctor blade" or "casting") for coating, roller coating, curtain slit extrusion coating, or dip coating.

[0094] In order to give the mixture according to the invention a viscosity suitable for coating techniques commonly used in the manufacture of electrodes, and thus to allow it to be deposited on a substrate, it is advantageous to use the mixture according to the invention in the form of a colloidal suspension or paste with a solid content of less than 30% by weight.

[0095] According to the applicant's findings, when the average diameter of the aggregates or clusters of nanoparticles is 50 nm to 900 nm, preferably 100 nm to 800 nm (more preferably 100 nm to 400 nm), a mesoporous layer with an average mesopore diameter of 2 nm to 100 nm is obtained during subsequent steps of the method.

[0096] According to the invention, the porous layer can be deposited by inkjet printing or by coating methods (particularly dip coating, roll coating, curtain coating, slot extrusion coating, or doctor blade coating) in the form of a highly concentrated suspension of an aggregate or agglomerate of nanoparticles comprising at least one oxide electronic conductor material precursor and an active material P.

[0097] Porous electrode layers can also be deposited by electrophoretic deposition, but the mixture according to the invention is advantageously used in the form of a low-concentration suspension containing at least one oxide electronic conductor material precursor and an agglomeration of nanoparticles of active material P.

[0098] Depositing mixtures according to the invention using electrophoresis, extrusion, additive manufacturing, dip coating, inkjet coating, roll coating, curtain coating, doctor blade coating, or slot extrusion coating are simple, safe, easy to implement, and industrially feasible methods that yield a uniform final porous layer. Electrophoretic deposition allows for the uniform deposition of layers on large surfaces at high deposition rates. Compared to electrophoretic deposition techniques, coating techniques, particularly those mentioned above, simplify bath management because particles in the suspension are not depleted during deposition. Deposition via inkjet printing enables localized deposition.

[0099] Thick porous layers, preferably with a thickness of 50 to 400 μm, can be produced in a single step by roller coating, curtain coating, slot extrusion coating, or by doctor blade coating (i.e., with a blade) or by extrusion.

[0100] The performance of the techniques and deposition methods for depositing colloidal suspensions or pastes (inks) according to the invention must be adapted to the viscosity of the colloidal suspensions or pastes (inks) used, and vice versa.

[0101] The substrate is advantageously an intermediate substrate or a substrate that can be used as a current collector.

[0102] 4.1 Substrate capable of serving as a current collector In a first embodiment, the substrate is a substrate capable of acting as an electron current collector and is advantageously compatible with the heat treatment used in the method according to the invention. The substrate can advantageously be a metallic substrate or a substrate made of electronically conductive carbon, particularly a substrate based on graphite, graphene, and / or carbon nanotubes. The substrate on which the mixture according to the invention is deposited in the form of a colloidal suspension or paste (ink) ensures the current collector function of the electrode. The mixture according to the invention in the form of a colloidal suspension or paste (ink) can be deposited on one or both sides of the substrate, particularly by the deposition techniques described above.

[0103] The current collector in an electrochemical device using the electrode according to the invention can be a substrate stable within the potential operating range of the electrochemical device. In a battery employing the electrode according to the invention, the current collector must be a substrate stable within a potential range (preferably 2.5V to 5V for the cathode and 0V to 2.5V for the anode) relative to the potential of lithium. Advantageously, a metal substrate, such as a metal strip (i.e., a laminated metal sheet), is chosen. The substrate can be made, in particular, of tungsten, molybdenum, chromium, titanium, tantalum, zirconium, niobium, stainless steel, or alloys of two or more of these materials. Such metal substrates are quite expensive and significantly increase the cost of the battery. Tungsten, molybdenum, chromium, titanium, tantalum, zirconium, niobium, stainless steel, and their alloys are particularly resistant to high-temperature heat treatment; therefore, they are particularly suitable as sinterable electrode substrates. The reason for using these heat-resistant substrates is that deposits, preferably thin deposits, can be sintered directly onto the substrate.

[0104] The substrate, capable of acting as an electron current collector, can also be coated with a conductive or semi-conductive oxide before depositing the mixture according to the invention in the form of a colloidal suspension or paste (ink). This allows for the protection, in particular, of less expensive substrates, such as those made of copper, nickel, aluminum, and carbon, especially those in the form of graphite. Therefore, these less expensive substrates can be used as electrode substrates, especially due to their cost. This can involve conductive carbon sheets (typically made of graphite), metal sheets, or metallized (i.e., non-metallic sheets covered with a metal layer). The substrate is preferably selected from strips made of copper, nickel, molybdenum, tungsten, tantalum, chromium, niobium, zirconium, titanium, and alloy strips containing at least one of these elements. Stainless steel can also be used. These substrates have the advantages of stability and heat resistance over a wide potential range.

[0105] Copper, nickel, molybdenum, and their alloys are preferred as anode substrates. Carbon-based substrates, particularly those in the form of graphite, and substrates based on nickel-chromium, stainless steel, chromium, titanium, aluminum, tungsten, molybdenum, tantalum, zirconium, niobium, or alloys containing at least one of these elements, are preferred as cathode electron current collector substrates. These anode and / or cathode substrates may or may not be coated with an electrochemically inert conductive layer. Such a layer can be prepared by depositing nitrides, carbides, graphite, gold, palladium, and / or platinum.

[0106] The mixture according to the invention, in the form of a colloidal suspension or paste (ink), can be deposited on one or both sides of a substrate capable of acting as a current collector. The layer deposited on the substrate is then dried to obtain a porous layer containing at least one precursor of an electrode active material P and an active electronic conductor material.

[0107] Then, one or more oxide electronic conductor material precursors are converted into oxide electronic conductor materials on the porous dried layer, which is initially deposited on one or both sides of a substrate that can act as a current collector.

[0108] 4.2 Intermediate substrate According to the second embodiment, the mixture of the present invention, which includes at least one precursor of electrode active material P and active material electronic conductor (ink) in the form of a colloidal suspension or paste, is not deposited on a substrate that can be used as a current collector, but rather on an intermediate substrate that is typically used temporarily.

[0109] In this embodiment, the mixture according to the invention is deposited on one side of an intermediate substrate in the form of a colloidal suspension or paste (ink) so that the obtained layer can be easily separated from the intermediate substrate thereafter.

[0110] In particular, a fairly thick layer, referred to as a "green sheet," can be deposited from a mixture according to the invention in the form of a suspension or paste of aggregates and / or agglomerates of nanoparticles containing at least one oxide electronic conductor material precursor and electrode active material P, preferably from a concentrated suspension (i.e., less fluid, preferably paste) of aggregates and / or agglomerates of nanoparticles containing at least one oxide electronic conductor material precursor and electrode active material P. These thick layers can be deposited by any suitable method, particularly by inkjet printing, extrusion, additive manufacturing, spraying, flexographic printing, coating methods (preferably blade coating, roll coating, curtain coating, slot extrusion coating, or dip coating).

[0111] Methods for depositing nanoparticles using dip coating, inkjet printing, roll coating, screen coating, slot extrusion coating, extrusion, additive manufacturing, spraying, flexographic printing, or doctor blade coating are simple, safe, easy to implement, and industrialize, and can produce uniform deposits. Inkjet printing allows for the localized deposition of mixtures according to the invention in the same manner as doctor blade deposition under a mask. Thick layers can be obtained in a single step using roll coating, screen coating, slot extrusion coating, dip coating, extrusion, additive manufacturing, or doctor blade coating technologies.

[0112] The intermediate substrate can be a flexible substrate, which can be a polymer sheet, such as polyethylene terephthalate (PET). In this second embodiment, the deposition step is advantageously performed on one side of the intermediate substrate to facilitate subsequent separation of the layer from the substrate. In this second embodiment, the layer is separated from the substrate after drying and before any high-temperature heat treatment. The thickness of the dried layer is advantageously less than or equal to 5 mm, advantageously from about 1 µm to about 600 µm. The thickness of the dried layer is advantageously less than 500 μm, preferably from about 3 μm to about 400 μm, more preferably from 3 μm to 300 μm.

[0113] In the second embodiment, a method for producing electrodes for an electrochemical device (e.g., a battery) uses an intermediate substrate preferably made of a polymer (e.g., PET) and produces a strip called a "green tape". After drying, the green tape is then separated from its substrate; subsequently, the green tape forms a self-supporting plate or sheet (here, in the following text, the term "plate" is used, regardless of its thickness).

[0114] Then, the process of converting one or more oxide electronic conductor material precursors into oxide electronic conductors is carried out on these self-supporting porous plates or sheets.

[0115] 5. Convert one or more oxide electronic conductor material precursors present in the porous drying layer into oxide electronic conductor materials. A self-supporting porous drying layer or porous plate containing at least one precursor of the electrode active material P and the active material electronic conductor is preferably heat-treated at a sufficient temperature in air or an oxidizing atmosphere to convert the one or more oxide electronic conductor material precursors in question into oxide electronic conductor materials. The region forming the electrode active material P is at least partially covered by a coating of electronic conductor material, preferably an oxide electronic conductor material coating, more preferably SnO2, aluminum-doped ZnO (ZnO:Al, preferably having a molar ratio of 1:0.015 to 1:0.05 Zn:Al), In2O3, Ga2O3, MoO3, SrMoO3, a mixture containing two of these oxides (e.g., indium tin oxide corresponding to a mixture of indium oxide (In2O3) and tin oxide (SnO2), a mixture of three of these oxides, a mixture of four of these oxides, a mixture of five of these oxides, or a mixture of six of these oxides, distributed in a fully distributed manner throughout the internal volume and surface of the electrode.

[0116] This heat treatment, preferably carried out in an oxidizing atmosphere, can eliminate organic components, i.e., perform debinding. Depending on the properties of the electrode active material P used and the temperature used to convert the one or more oxide electronic conductor material precursors under discussion into oxide electronic conductor materials, this heat treatment can also solidify the layer or porous plate, which will be explained in detail in the following sections.

[0117] Regarding the prior art, particularly porous electrodes comprising a carbon coating on and within the pores of the electrode as described in application WO2021 / 220174, the presence of regions of electrode active material P, preferably covered by a coating of oxide electronic conductor material in a perfectly distributed manner throughout the entire internal volume and surface of the electrode, endows the electrode with better electrochemical performance at high temperatures and significantly increases the stability of the electrode. The fact that this single three-dimensional structure (including regions of electrode active material P covered at least partially by a coating of oxide electronic conductor material throughout the entire internal volume and surface of the electrode, preferably including regions of electrode active material P covered by a coating of oxide electronic conductor material throughout the entire internal volume and surface of the electrode) particularly gives rise to the superior performance of the final electrode. More specifically, the presence of an oxide electronic conductor material coating covering at least part of the electrode's internal volume and surface, preferably covering the active material P-regions, can improve the electrode's final performance, particularly its voltage and temperature stability, and its electrochemical stability, especially when it comes into contact with a liquid electrolyte, to reduce the electrode's polarization resistance, even when the electrode is thick. When the active material resistance is too high in thick and / or porous layers, the use of an oxide electronic conductor material (particularly In₂O₃, SnO₂, aluminum-doped ZnO (ZnO:Al, preferably with a molar ratio of 1:0.015 to 1:0.05), Ga₂O₃, or one or more of these oxides or mixtures of these doped oxides) in the electrode volume is particularly advantageous.

[0118] The electrode according to the invention is porous, preferably mesoporous, and advantageously has a large specific surface area. Increasing the specific surface area of ​​the electrode increases the exchange surface area, thereby increasing the power of the battery, but also accelerates parasitic reactions. The presence of these electronically conductive coatings in the form of oxides in the electrode volume will block these parasitic reactions.

[0119] Furthermore, due to their very large specific surface area, the effect of these oxide-form electronic conductor coatings on the electronic conductivity of the electrode is more pronounced than in conventional electrodes with smaller specific surface areas, even if the deposited conductor coating has a lower thickness. These oxide electronic conductor coatings, deposited within the volume of the porous electrode layer, impart excellent electronic conductivity to the electrode, especially when the porous layer is formed from an electrode active material with poor electronic conductivity. This oxide electronic conductor material layer can improve the conductivity of the electrode while limiting electrode dissolution, thus enabling increased battery power; this is especially true due to the lower thickness of the oxide electronic conductor material coating with the electrode active material region P.

[0120] This is essentially a single structure of porous electrodes produced according to the method of the present invention (including the electrode active material P region covered by a coating of oxide electronic conductor material on the entire internal volume of the electrode and on the surface), which makes it possible to improve the final performance of the electrode, especially to obtain thick electrodes without increasing the internal resistance of the electrode.

[0121] The thickness of the oxide electronic conductor material coating covering the P region of the electrode active material is less than 10 nm, preferably less than 7 nm, more preferably less than 5 nm, even more preferably 5 nm to 3 nm, and even more preferably less than 3 nm. The oxide electronic conductor material coating advantageously has an optimal thickness throughout the entire internal volume of the electrode; this coating must be thick enough to improve electronic conduction and thin enough not to impede ion conduction within the electrode, and ultimately not to degrade the performance of the energy storage device or energy generation device (such as a battery). Furthermore, due to the large specific surface area of ​​the electrode, this coating imparts good electronic conductivity to the electrode.

[0122] Advantageously, the electronic conductor material may be an oxide electronic conductor material, preferably selected from: - Tin oxide (SnO2), aluminum-doped zinc oxide (ZnO:Al) (preferably with a molar ratio of 1:0.015 to 1:0.05 Zn:Al), indium oxide (In2O3), gallium oxide (Ga2O3), molybdenum oxide (MoO3), strontium molybdenum oxide (SrMoO3), mixtures of two of these oxides (e.g., indium tin oxide corresponding to a mixture of indium oxide (In2O3) and tin oxide (SnO2), mixtures of three of these oxides, mixtures of four of these oxides, mixtures of five of these oxides, or mixtures of six of these oxides. - A zinc oxide-based doped oxide, preferably doped with gallium (Ga) and / or aluminum (Al) and / or boron (B) and / or beryllium (Be), and / or chromium (Cr) and / or cerium (Ce) and / or titanium (Ti) and / or indium (In) and / or cobalt (Co) and / or nickel (Ni) and / or copper (Cu) and / or manganese (Mn) and / or germanium (Ge) and / or molybdenum (Mo). - Indium oxide-based doped oxides, preferably doped with tin (Sn) and / or gallium (Ga) and / or chromium (Cr) and / or cerium (Ce) and / or titanium (Ti) and / or indium (In) and / or cobalt (Co) and / or nickel (Ni) and / or copper (Cu) and / or manganese (Mn) and / or germanium (Ge) and / or molybdenum (Mo). - Doped tin oxide, preferably doped with arsenic (As) and / or fluorine (F) and / or nitrogen (N) and / or niobium (Nb) and / or phosphorus (P) and / or antimony (Sb) and / or aluminum (Al) and / or titanium (Ti) and / or gallium (Ga) and / or chromium (Cr) and / or cerium (Ce) and / or indium (In) and / or cobalt (Co) and / or nickel (Ni) and / or copper (Cu) and / or manganese (Mn) and / or germanium (Ge) and / or molybdenum (Mo). - Molybdenum oxide-based doped oxides, preferably doped with lithium (Li) and / or sodium (Na) and / or potassium (K) and / or beryllium (Be) and / or magnesium (Mg) and / or calcium (Ca) and / or scandium (Sc) and / or titanium (Ti) and / or vanadium (V) and / or chromium (Cr) and / or manganese (Mn) and / or iron (Fe) and / or cobalt (Co) and / or nickel (Ni) and / or copper (Cu) and / or zinc. (Zn) and / or gallium (Ga) and / or germanium (Ge) and / or arsenic (As) and / or rubidium (Rb) and / or cesium (Cs) and / or yttrium (Y) and / or zirconium (Zr), and / or strontium (Sr) and / or niobium (Nb) and / or tritium (T) and / or rhenium and / or iridium (Ir) and / or platinum (Pt) and / or gold (Au) and / or mercury (Hg) and / or lead (Pb) and / or bismuth (Bi).

[0123] 6. Consolidate a porous layer comprising electrode active material P and oxide electronic conductor material to obtain a porous, preferably mesoporous, electrode.

[0124] The porous layer or self-supporting porous plate can then be heat-treated, preferably in an oxidizing atmosphere, to remove organic components, if desired. The porous layer or self-supporting porous plate can then be consolidated. This consolidation can be achieved by pressing and / or heat treatment, i.e., by heat treatment (heating), by heat treatment followed by mechanical treatment, and optionally by thermomechanical treatment (typically hot pressing). In a highly advantageous embodiment of the invention, this treatment results, on the one hand, in the partial agglomeration of primary nanoparticles into aggregates or clusters, and on the other hand, in the presence of an oxide electronic conductor material coating, in the partial agglomeration between adjacent aggregates or clusters; this phenomenon is referred to as “necking” or “neck formation.” It is characterized by the partial agglomeration of two contacting particles, which remain separated but are connected by (restricted) necks. Lithium ions and electrons are mobile within these necks and can diffuse from one particle to another without encountering grain boundaries. The nanoparticles are bound together to ensure electron conduction from one particle to another. Adjacent aggregates or clusters are bound together by the presence of an oxide electronic conductor coating to ensure electron conduction from one aggregate or cluster to another. Electronic conduction occurs in two distinct ways, particularly through nanoparticles of the electrode active material P(1) bonded together, and through adjacent aggregates or clusters bonded together by the oxide electronic conductor material (2); this in Figure 1 It is shown schematically in the middle.

[0125] Therefore, a rigid mesoporous membrane without an organic binder is formed from primary nanoparticles of electrode active material P (1) and oxide electronic conductor material (2), forming a three-dimensional network with high ion mobility and electronic conductivity; this network includes interconnected pores, preferably mesoporous. The resulting porous layer, preferably a mesoporous layer, is ideally suited for impregnating the pores of the electrode with an ion conductor material, which penetrates to the depth of the open porous structure of the layer.

[0126] The temperature required to achieve "necking" depends on the material; given the diffusion nature of the phenomenon, the duration of the treatment also depends on the temperature. This method can be called sintering; depending on its duration and temperature, more or less noticeable agglomeration (necking) is obtained, which affects the porosity. Thus, electrodes with desired porous or mesoporous ceramic structures with controllable porosity can be obtained while maintaining perfectly uniform channel dimensions. During this thermomechanical or thermal treatment, the electrode layer will be free of any organic components and residues (such as nanoparticles, binders, and the liquid phase of a suspension of optional surfactant products): it becomes an inorganic (ceramic) layer.

[0127] The thickness of these porous electrodes or plates centered in this manner is advantageously less than or equal to 5 mm, advantageously from about 1 µm to about 500 µm. The thickness of the sintered porous plate is advantageously from 2 µm to 400 μm, preferably from 2 μm to about 300 μm, and preferably from 3 μm to 200 μm.

[0128] According to the second embodiment, in order to obtain a porous electrode disposed on a substrate capable of acting as a current collector, a conductive sheet is also provided, which has a thin layer of conductive adhesive (loaded with graphite) or a sol-gel deposit filled with conductive particles on at least one side, preferably on both sides. The thin layer preferably has a thickness of less than 1 μm. This electronically conductive sheet can be a metal strip or a graphite sheet.

[0129] When the electronically conductive sheet is metallic, it is preferably a laminated sheet, i.e., obtained by lamination. Optionally, a final annealing can be performed after lamination; in metallurgical terms, this annealing can be (fully or partially) softening annealing or recrystallization. Plates obtained by electrolytic deposition, such as electrodeposited copper or nickel sheets, can also be used.

[0130] Then, after consolidation (i.e., sintering), the conductive sheet is placed on a plate or inserted between two previously obtained plates. The assembly is then advantageously pressed such that the thin intermediate layer of the conductive adhesive promotes adhesion between the plate and the substrate, forming a plate / substrate or plate / substrate / plate assembly to obtain a rigid, monolithic subassembly.

[0131] One advantage of the second implementation is that it allows the use of cheaper substrates, such as aluminum strips, copper strips, or graphite strips. More specifically, these strips cannot withstand the heat treatment required for consolidating the deposited layers; the fact that they are bonded to the board after heat treatment also prevents them from oxidizing.

[0132] The resulting plates / substrates or plates / substrates / plate assemblies can be used to produce electrochemical devices, such as batteries.

[0133] Optionally, the porous electrode according to the invention, preferably a self-supporting porous plate, can be impregnated with an ionicly conductive phase (i.e., a phase comprising at least one ionic conductor material, such as an ionic conductor polymer or an ionic liquid polymer). This ionic conductor material may also be electronically conductive. The ionic conductor material can be of different types. They can be liquids in gel form or solids. Impregnation of solid ionic conductors is advantageously carried out using ionic conductors in a molten state or dissolved in a solvent, which is subsequently evaporated. The ion-conducting phase may include or be an ion-conducting polymer, preferably selected from polyethylene oxide (PEO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(propylene carbonate) (PPC), poly(ethylene carbonate) (PEC), poly(vinyl carbonate) (PVC), polyvinylidene fluoride (PVDF), polypropylene glycol (PPG), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polydimethylsiloxane (PDMS), poly(ε-caprolactone) (PCL), and poly(trimethylene carbonate) (PTMC).

[0134] The presence of an ion-conducting polymer in the pores of the porous electrode, preferably in the pores of a self-supporting porous plate, provides better mechanical rigidity. Using the porous electrode impregnated with the ion-conducting polymer according to the invention in energy storage devices or energy production devices such as batteries can increase their service life.

[0135] Optionally, a layer that is electronically insulating and has good ionic conductivity can be deposited on top of the porous electrode according to the invention; the thickness of the deposited layer is typically from about 0.5 nm to 20 nm, preferably less than 5 nm, and even more preferably less than 2 nm.

[0136] The ion-conducting and electrically insulating layer can be inorganic or organic in nature. More specifically, inorganic layers that can be used include, for example, lithium-ion oxide, phosphate, or borate conductors, and organic layers that can be used include polymers (e.g., optionally lithium-containing PEO or tetrafluoroethylene sulfonate copolymers, such as Nafion™, CAS No. 31175-20-9). This ion-conducting and electrically insulating layer must be in stable contact with the electrode on which it is deposited. Lithium-ion borate conductors are preferably used on the cathode.

[0137] This ion-conducting and electrically insulating layer makes it possible to restrict the dissolution of ions from the electrode and their migration into the electrolyte. It should be understood that in electrodes made of LiMn2O4, manganese is at risk of dissolving in certain liquid electrolytes, especially at high temperatures.

[0138] When the electrode according to the invention is covered with an ion-conducting layer, as mentioned above, it is the latter that primarily ensures the protective function (in particular, preventing electrode dissolution).

[0139] In summary, according to the invention, the presence of a coating of oxide electronic conductor material covering at least partially the entire internal volume of the electrode and on the surface of the porous electrode, preferably in regions of the electrode active material P covered with the oxide electronic conductor material coating, allows for at least an increase in electronic conductivity, and, depending on the properties of the oxide electronic conductor material, can advantageously protect the electrode from dissolving in the electrolyte at high temperatures. According to the invention, both effects are achieved solely by a single arrangement of oxide electronic conductor material throughout the entire internal volume and on the electrode surface, or, according to the invention, such a specific arrangement of oxide electronic conductor material throughout the entire internal volume of the electrode is insufficient to achieve both effects. In this case, a layer, for example, ionically conductive and electronically insulating, can be deposited on and within the pores of the electrode according to the invention to obtain additional protection at high temperatures.

[0140] According to the first and second embodiments, a porous electrode according to the invention is obtained, which is disposed on or located on either side of a metal substrate serving as an electron current collector. The electrode / substrate / electrode sub-assemblies thus obtained through the first or second embodiments can be used to produce electrochemical devices such as batteries, particularly microcells. Assembly by thermal bonding can also be performed on components of a stacked and thermo-pressed electrochemical device (e.g., a battery, particularly a microcell); in this case, a multilayer stack is assembled, including a first anode according to the invention, its metal substrate, a second anode according to the invention, a solid electrolyte layer or electrolyte membrane, a first cathode according to the invention, its metal substrate, a second cathode according to the invention, a new solid electrolyte layer or a new electrolyte membrane, etc.

[0141] This electrode / substrate / electrode subassembly can be used to produce electrochemical devices such as batteries (especially microcells). Regardless of the implementation of the electrode / substrate / electrode subassembly, an electrolyte membrane or electrolyte separator is then deposited on the latter. The necessary cutting is then performed to produce a battery with multiple basic cells, and the subassemblies are then stacked (typically "head to tail") and hot-pressed to bond the anode and cathode together at the solid electrolyte.

[0142] Alternatively, the cutting required for producing a battery with multiple basic cells can be performed before depositing an electrolyte membrane or electrolytic separator on each anode / substrate / anode and cathode / substrate / cathode sub-assembly. The anode / substrate / anode sub-assembly and / or cathode / substrate / cathode sub-assembly are then covered with the electrolyte membrane or electrolytic separator, and the sub-assemblies are stacked and hot-pressed to bond the anode and cathode together at the electrolyte membrane or electrolytic separator. If desired, the resulting stack is impregnated with an electrolyte, preferably a phase carrying lithium, sodium, or potassium ions.

[0143] In the two alternatives just proposed, bonding by hot pressing can be performed at relatively low temperatures, particularly when the electrode according to the invention is impregnated with an ion-conducting material, which can be an ion-conducting polymer or an ion liquid polymer. For this reason, no oxidation of the substrate metal layer was observed.

[0144] Example Example 1: Production based on LiMn2O4 cathode according to the present invention According to Liddle et al.'s article titled "A new one-pot hydrothermal synthesis and electrochemical characterization of Li 1+x Mn 2-y The method described in the article "LiMn2O4 nanoparticles prepared by hydrothermal synthesis using the method described in Volume 3, Energy & Environmental Science (2010), pp. 1339-1346": 14.85 g of LiOH·H₂O was dissolved in 500 mL of water. 43.1 g of KMnO₄ was added to this solution, and the liquid phase was poured into an autoclave. While stirring, 28 mL of isobutyraldehyde and water were added until a total volume of 3.54 L was obtained. The autoclave was then heated to 180°C and maintained at this temperature for 6 hours. After slow cooling, a suspension of a black precipitate in the solvent was obtained. This precipitate was subjected to a series of centrifugation steps in water—redispersing it in water—until an aggregated suspension with a conductivity of approximately 300 µS / cm and a zeta potential of -30 mV was obtained. The obtained aggregates consisted of aggregated primary particles with a size of 10 to 20 nm. The obtained aggregates had a spherical shape and an average diameter of approximately 150 nm; they were characterized by X-ray diffraction and electron microscopy.

[0145] 1 g of polyvinylpyrrolidone (PVP) with a molecular weight of 55,000 g / mol was added to 50 mL of distilled water at 40°C, and then 3 g of tin oxalate SnC2O4 was added to the PVP aqueous solution.

[0146] The LiMn2O4 suspension was reconcentrated by centrifugation, and the particles were redispersed in a necessary volume of water to obtain a 16 wt% paste. Then, the volume of an aqueous solution of PVP and tin acetate (corresponding to a 10 wt% ratio of tin acetate to LiMn2O4) and the required amount of water were added to the LiMn2O4 suspension of nanoparticle aggregates to obtain a final aggregate suspension with a solids content of 10%.

[0147] The resulting ink was applied to a 5 µm thick stainless steel (316L) strip. The resulting layer was dried in a temperature-controlled oven. The thickness of the resulting layer was approximately 6 µm.

[0148] The layer was then heat-treated in air at 600°C for 5 hours. This was done to convert the precursor tin acetate of the oxide electronic conductor material into SnO2, thus transforming it into an oxide electronic conductor material and removing reaction byproducts. Furthermore, the presence of the formed SnO2 oxide electronic conductor material was used to bond the primary nanoparticles together, to bond adjacent aggregates together, to improve adhesion to the substrate, and to facilitate the recrystallization of LiMn2O4. The resulting porous layer had an open porosity of approximately 45% by volume and pores with sizes ranging from 10 nm to 20 nm.

[0149] Example 2: Based on Li4Ti5O according to the present invention 12 Production of mesoporous anodes Li4Ti5O was prepared by glycothermal synthesis. 12 Nanoparticle suspension: Pour 190 mL of 1,4-butanediol into a beaker and add 4.25 g of lithium acetate while stirring. Keep the solution unstirred until the acetate is completely dissolved. Under an inert atmosphere, take 16.9 g of titanium butoxide and introduce it into the acetate solution. Then stir the solution for several minutes and transfer it to an autoclave pre-filled with another 60 mL of butanediol. Then close the autoclave and purge with nitrogen for at least 10 minutes. Then heat the autoclave to 300°C at a rate of 3°C / min and maintain this temperature for 2 hours with stirring. Finally, allow it to cool while continuing to stir.

[0150] A suspension of a white precipitate in a solvent was obtained. This precipitate was subjected to a series of centrifugation steps followed by redispersion in ethanol to obtain a pure colloidal suspension with low ionic conductivity. It contained aggregates of approximately 150 nm formed from primary particles of 10 nm. The zeta potential was approximately -45 mV. The product was characterized by X-ray diffraction and electron microscopy.

[0151] 1 g of polyvinylpyrrolidone (PVP) with a molecular weight of 55,000 g / mol was added to 50 mL of ethanol at 40°C, and then 3 g of tin oxalate was added to the PVP solution.

[0152] Then, to the Li4Ti5O 12 The volume of PVP and tin acetate aqueous solution (corresponding to a 10% mass ratio of tin acetate to LiMn2O4) was added to the suspension of nanoparticle aggregates. Ethanol was evaporated until the suspension of aggregates had a 10% solids content. The resulting ink was applied to a 5 µm thick stainless steel (316L) strip. The resulting layer was dried in a temperature and humidity controlled oven to avoid cracking during drying. The ink deposition and drying were then repeated to obtain a layer approximately 4 μm thick. This layer was then heat-treated in air at 600 °C for 5 hours. This heat treatment enables the tin acetate precursor of the oxide electronic conductor material to be converted to SnO2, i.e., to the oxide electronic conductor material, eliminating reaction byproducts and thus forming Li4Ti5O containing a uniform SnO2 coating. 12 A porous layer of nanoparticle aggregates is formed, and this layer is consolidated, i.e., the primary nanoparticles are bonded together and adjacent aggregates are bonded together by the presence of the formed oxide electronic conductor material SnO2, in order to improve the Li4Ti5O coated with SnO2. 12 The adhesion of nanoparticle aggregates to the substrate and the improvement of Li4Ti5O 12 Recrystallization.

[0153] Example 3: Production of a battery using the porous cathode and porous anode according to the present invention a. Preparation of Li3PO4 nanoparticle suspension Two solutions were prepared. 11.44 g of CH3COOLi,2H2O was dissolved in 112 ml of water, and then 56 ml of water was added to the medium with vigorous stirring to obtain solution A. 4.0584 g of H3PO4 was diluted in 105.6 ml of water, and then 45.6 ml of ethanol was added to this solution to obtain the second solution, hereinafter referred to as solution B.

[0154] Solution B was then added to solution A under vigorous stirring. Using an Ultraturrax™ homogenizer, the resulting solution, which was very clear after the bubbles disappeared, was added to 1.2 liters of acetone to homogenize the medium. A suspension of white precipitate was immediately observed in the liquid phase.

[0155] Homogenize the reaction medium for 5 minutes, then maintain magnetic stirring for 10 minutes. Decant for 1 to 2 hours. Discard the supernatant, then centrifuge the remaining suspension at 6000 rpm for 10 minutes. Add 300 ml of water to place the precipitate in the suspension (using a sonotrode with magnetic stirring). Under vigorous stirring, add 125 ml of 100 g / L sodium tripolyphosphate solution to the resulting colloidal suspension. The suspension then becomes more stable. Ultrasonicate the suspension using a sonotrode. Centrifuge the suspension at 8000 rpm for 15 minutes. Redisperse the particles in 150 ml of water. Centrifuge the resulting suspension again at 8000 rpm for 15 minutes, and redisperse the resulting particles in 12 ml of water.

[0156] This yields a suspension in water of aggregates approximately 100 nm in size, formed from primary particles of Li3PO4 with a diameter of 10 nm.

[0157] b. A porous inorganic layer is generated on the pre-formed anode and cathode layers by the Li3PO4 nanoparticle suspension described in section a) above.

[0158] A porous Li3PO4 thin layer was then deposited from the previously obtained suspension of Li3PO4 nanoparticles by coating the surfaces of the pre-formed anode and cathode to obtain a layer with a thickness of approximately 3 μm. The layer was dried in air at 120°C to remove any trace organic residues and then calcined in air at 350°C for 1 hour.

[0159] c. Production of electrochemical batteries After depositing 3 µm porous Li3PO4 on each pre-formed electrode (see Examples 1 and 2), the two subsystems were stacked to bring the Li3PO4 films into contact. The stack was then hot-pressed under vacuum.

[0160] For this purpose, the stack was subjected to a pressure of 1.5 MPa, and then at 10... -3 The platen under the press was dried under vacuum for 30 minutes. Then the press platen was heated to 450°C at a rate of 4°C / second. The stack was then hot-pressed at 450°C and 45MPa for 1 minute, and then the system was cooled to ambient temperature.

[0161] After assembly, a rigid multilayer system is obtained, consisting of one or more assembled battery cells.

[0162] The component was then immersed in an electrolyte solution containing 0.7 MPYR14 TFSI of LiTFSI. The electrolyte immediately entered the pores via capillary action. The system was immersed for 1 minute, and then the surface of the battery stack was dried with an N2 air knife.

Claims

1. A method for producing a porous electrode, particularly a porous electrode for use in an energy storage device or an energy generation device, the electrode being a porous layer comprising at least one electrode active material P and an oxide electronic conductor material, the electrode being binder-free, having a porosity of 25 vol% to 60 vol%, preferably 25 vol% to 50 vol%, and pores with an average diameter of less than 100 nm, the method being characterized in that it comprises: (a) A colloidal suspension or paste comprising a substrate, at least one oxide electronic conductor material precursor, and primary nanoparticles comprising at least one electrode active material P, wherein the primary median diameter D of the primary nanoparticles is... 50 The median diameter D of the aggregates or agglomerates is 2 nm to 400 nm, preferably 2 nm to 100 nm, more preferably 2 nm to 60 nm. 50 The nm range is 50 nm to 900 nm, preferably 100 nm to 800 nm. It should be understood that the substrate can be a substrate capable of acting as a current collector, or an intermediate substrate. (b) The one or more oxide electronic conductor material precursors provided in step (a) are mixed with the colloidal suspension or paste of an aggregate or agglomerate containing at least one electrode active material P to form a mixture. (c) A mixture layer is formed from the mixture obtained at the end of step (b) by a method selected from the group consisting of: electrophoresis, additive manufacturing, extrusion, printing (preferably inkjet printing or flexographic printing), coating (preferably blade coating, roller coating, curtain coating, dip coating or slot extrusion coating). (d) Drying the layer obtained in step (c) to obtain a dried layer, wherein, if necessary, the dried layer is separated from its intermediate substrate after drying step (d). (e) Converting the one or more oxide electronic conductor material precursors into an oxide electronic conductor material, such that the dried layer contains the oxide electronic conductor material. (f) The layer is solidified by heating and / or mechanical treatment, preferably by sintering, to obtain a porous, preferably mesoporous electrode. It should be understood that steps (e) and (f) can be performed in the same heat treatment process.

2. The method for manufacturing a porous electrode according to claim 1, characterized in that... Step (b) is performed by contacting a colloidal suspension or paste of the primary nanoparticles containing at least one electrode active material P provided in step (a) with a liquid phase containing at least one precursor of the oxide electronic conductor material, wherein the conversion of the one or more oxide electronic conductor material precursors to the oxide electronic conductor material during step (e) is performed by heat treatment such as calcination, preferably in air or an oxidizing atmosphere.

3. The method for manufacturing a porous electrode according to claim 1 or 2, characterized in that, Following step (f), the pores of the porous electrode are impregnated with an electrolyte, preferably with a phase containing lithium, sodium, or potassium ions, wherein the electrolyte is selected from: - An electrolyte consisting of at least one aprotic solvent and at least one lithium, sodium, or potassium salt; - An electrolyte consisting of at least one ionic liquid and at least one lithium, sodium, or potassium salt; - A mixture of at least one aprotic solvent, at least one ionic liquid, and at least one lithium, sodium, or potassium salt; - An ionic liquid polymer; - A polymeric ionic conductor made by adding at least one lithium, sodium, or potassium salt; and - A polymeric ionic conductor made by adding a liquid electrolyte to a polymeric phase or porous structure of a porous electrode, or by using an ionic conductor polymer, wherein the ionic conductor polymer is preferably selected from polyethylene oxide (PEO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(propylene carbonate) (PPC), poly(carbonate) (PEC), poly(ethylene carbonate) (PVC), polyvinylidene fluoride (PVDF), polypropylene glycol (PPG), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polydimethylsiloxane (PDMS), poly(ε-caprolactone) (PCL), and poly(trimethylene carbonate) (PTMC).

4. The method for preparing a porous electrode according to any one of claims 1 to 3, characterized in that, The one or more oxide electronic conductor material precursors are selected from organic salts containing one or more metal elements, which can form oxide electronic conductors after heat treatment such as calcination, and are characterized in that the conversion to an electronic conductor material is carried out by heat treatment, such as calcination, preferably in air or an oxidizing atmosphere, and these organic salts are preferably selected from: - An alkoxide of at least one metallic element capable of forming an oxide electronic conductor after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination; - A nitrate of at least one metallic element capable of forming an oxide electronic conductor after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination; - An oxalate of at least one metallic element capable of forming an oxide electronic conductor after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination; and - An acetate of at least one metallic element capable of forming an oxide electronic conductor after heat treatment, preferably in air or an oxidizing atmosphere, such as calcination. - and / or preferably, the metallic element is selected from tin, zinc, indium, gallium, molybdenum, or a mixture of two, three, four, or five of these elements.

5. The method for producing a porous electrode according to any one of claims 1 to 4, characterized in that, The oxide electronic conductor material is selected from: tin oxide (SnO2), aluminum-doped zinc oxide (ZnO:Al), preferably having a molar ratio of 1:0.015 to 1:0.05 (Zn:Al), indium oxide (In2O3), gallium oxide (Ga2O3), molybdenum oxide (MoO3), strontium molybdenum oxide (SrMoO3), mixtures of two of these oxides, such as indium tin oxide corresponding to a mixture of indium oxide (In2O3) and tin oxide (SnO2), mixtures of three of these oxides, mixtures of four of these oxides, mixtures of five of these oxides, or mixtures of six of these oxides. - A zinc oxide-based doped oxide, preferably doped with gallium (Ga) and / or aluminum (Al) and / or boron (B) and / or beryllium (Be), and / or chromium (Cr) and / or cerium (Ce) and / or titanium (Ti) and / or indium (In) and / or cobalt (Co) and / or nickel (Ni) and / or copper (Cu) and / or manganese (Mn) and / or germanium (Ge) and / or molybdenum (Mo). - Indium oxide-based doped oxides, preferably doped with tin (Sn) and / or gallium (Ga) and / or chromium (Cr) and / or cerium (Ce) and / or titanium (Ti) and / or indium (In) and / or cobalt (Co) and / or nickel (Ni) and / or copper (Cu) and / or manganese (Mn) and / or germanium (Ge) and / or molybdenum (Mo), - doped tin oxides, preferably doped with arsenic (As) and / or fluorine (F) and / or nitrogen (N) and / or niobium (Nb) and / or phosphorus (P) and / or antimony (Sb) and / or aluminum (Al) and / or titanium (Ti) and / or gallium (Ga) and / or chromium (Cr) and / or cerium (Ce) and / or indium (In) and / or cobalt (Co) and / or nickel (Ni) and / or copper (Cu) and / or manganese (Mn) and / or germanium (Ge) and / or molybdenum (Mo), - based on oxide Molybdenum-doped oxides, preferably doped with lithium (Li) and / or sodium (Na) and / or potassium (K) and / or beryllium (Be) and / or magnesium (Mg) and / or calcium (Ca) and / or scandium (Sc) and / or titanium (Ti) and / or vanadium (V) and / or chromium (Cr) and / or manganese (Mn) and / or iron (Fe) and / or cobalt (Co) and / or nickel (Ni) and / or copper (Cu) and / or zinc (Z). n) and / or gallium (Ga) and / or germanium (Ge) and / or arsenic (As) and / or rubidium (Rb) and / or cesium (Cs) and / or yttrium (Y) and / or zirconium (Zr), and / or strontium (Sr) and / or niobium (Nb) and / or tritium (T) and / or rhenium and / or iridium (Ir) and / or platinum (Pt) and / or gold (Au) and / or mercury (Hg) and / or lead (Pb) and / or bismuth (Bi).

6. The method for manufacturing a porous electrode according to any one of claims 1 to 5, characterized in that, The porous electrode obtained at the end of step (f) has a diameter of 10 μm. 2 / g to 500 m 2 A specific surface area of ​​ / g and / or a thickness of 2 µm to 400 µm, preferably 2 µm to 300 µm, more preferably 3 µm to 200 µm.

7. The method for producing a porous electrode according to any one of claims 1 to 5, characterized in that, The porous electrode obtained at the end of step (f) has a diameter of 10 μm. 2 / g to 500 m 2 Specific surface area per g; and / or When the substrate is a substrate capable of acting as a current collector, it has a thickness of 2 μm to 20 μm, and / or When the substrate is an intermediate substrate, it has a thickness of 25 μm to 500 μm, preferably 50 μm to 400 μm.

8. The method for producing a porous electrode according to any one of claims 1 to 5, characterized in that, When the substrate is an intermediate substrate, after drying the layer, the layer is separated from the intermediate substrate in step (d) to form a porous plate.

9. The method for producing a porous electrode according to any one of claims 1 to 8, characterized in that... The colloidal suspension or paste provided in step (a) contains organic additives, such as ligands, stabilizers, binders or residual organic solvents, and the dried layer obtained at the end of step (d) according to any one of claims 1 to 7 or the porous plate according to claim 8 is subjected to heat treatment, preferably in an oxidizing atmosphere. It should be understood that this heat treatment and steps (e) and / or (f) can be performed in the same heat treatment step.

10. The method for producing a porous electrode according to any one of claims 1 to 9, wherein the electrode active material P is selected from the group (A) of the following: - Oxides LiMn2O4, Li 1+x Mn 2-x O4, where 0 <x< 0.15,LiCoO2、LiNiO2、LiMn 1.5 Ni 0.5 O4, LiMn 1.5 Ni 0.5-x X x O4, where X is selected from Al, Fe, Cr, Co, Rh, Nd, and other rare earth elements such as Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, and 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, and where 0 < x < 0.4, LiFeO2, LiMn 1 / 3Ni 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, where 0.6 ≤ y ≤ 0.85; 0 ​​≤ x + y ≤ 2; and M is selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sn, and Sb, or mixtures 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 the following: 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, and 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; and where M, N, and P are each at least one element selected from the group consisting of: Ti, Ta, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Zr, Y, Mo, Ru, Rh, Ce, 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 of the formula LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Li3V2(PO4)3, Li2MPO4F, wherein M = Fe, Co, Ni or a mixture of these different elements; LiMPO4F, wherein M = V, Fe, T or a mixture of these different elements; phosphates of the formula LiMM'PO4, wherein M and M' (M ≠ M') are selected from Fe, Mn, Ni, Co, V, for example LiFe x Co 1-x PO4, where 0 < x < 1; - Fe 0.9 Co 0.1 OF; FeF3; LiMSO4F, where M = Fe, Co, Ni, Mn, Zn, Mg; - 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, Li x V2O5, where 0 < x ≤ 2, Li x V3O8, where 0 < x ≤ 1.7, Li x TiS2, where 0 < x ≤ 1, lithium titanium oxysulfide Li x TiO y S z , where z = 2 - y, 0.3 ≤ y ≤ 1 and 0 < x ≤ 1, Li x WO y S z , where z = 2 - y, 0.3 ≤ y ≤ 1 and 0 < x ≤ 1, Li x CuS, where 0 < x ≤ 1, Li x CuS2, where 0 < x ≤ 1; Alternatively, choose from the following groups (B): Transition metal oxides: ○ Na x MO 2+z where M is selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ Na x M u / 2 M’ v / 2 O 2+z where u + v = 2 and M, M' are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ Na x M u / 3 M’ v / 3 M’’ w / 3 O 2+z where u + v + w = 3 and M, M', M'' are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ Na x Mn y Ni z Fe 0.1 Mg 0.1 O2, where 0.67≤x≤1.0; 0.5≤y≤0.7 and 0.1≤z≤0.3; - Prussian blue and / or Prussian blue analogues, abbreviated as PBA: ○ Na x M 1 [M 2 '(CN)6] y .nH2O, M 1 It is a transition metal or a transition metal alloy, M 2 ' is a transition metal, and the transition metal and the transition metal alloy are selected from Fe, Ni, Co and Mn, wherein 0≤x≤2; y≤1 and 0≤n≤12; - Polyanionic compounds: ○ Na x M2(XO4)3, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W, such as Na3V2(PO4)3; ○ Na x M3(XO4)2(X2O7), where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ Na x M(X2O7), where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ Na x M2(XO4)2F3, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ Na x M2(XO4)2F 3-y O y , where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and 0.07 ≤ y ≤ 0.12 and X = P, S, As, Si, Mo or W; ○ Na x M2O2(XO4)2F, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ Na x MXO4, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; Alternatively, choose from the following groups (C): -Transition metal oxides: ○ K x MO 2+z where M is selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ K x M u / 2 M’ v / 2 O 2+z , where u + v = 2 and M and M’ are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ K x M u / 3 M’ v / 3 M’’ w / 3 O 2+z where u + v + w = 3 and M, M', M'' are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, where z ≤ 0.3 and 0 < x ≤ 1, preferably 0 < x < 0.44 or 0.44 ≤ x ≤ 0.67 or 0.67 < x ≤ 1; ○ K x Mn y Ni z Fe 0.1 Mg 0.1 O2, where 0.67≤x≤1.0; 0.5≤y≤0.7 and 0.1≤z≤0.3; - Prussian blue and / or Prussian blue analogues, abbreviated as PBA: ○ L x M 1 [M 2 '(CN)6] y .nH2O, M 1 It is a transition metal or a transition metal alloy, M 2 ' is a transition metal, and the transition metal and the transition metal alloy are selected from Fe, Ni, Co and Mn, wherein 0≤x≤2; y≤1 and 0≤n≤12; - Polyanionic compounds: ○ K x M2(XO4)3, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W, for example Na3V2(PO4)3; ○ K x M3(XO4)2(X2O7), where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ K x M(X2O7), where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ K x M2(XO4)2F3, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ K x M2(XO4)2F 3-y O y , where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and 0.07 ≤ y ≤ 0.12 and X = P, S, As, Si, Mo or W; ○ K x M2O2(XO4)2F, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W; ○ K x MXO4, where 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc and X = P, S, As, Si, Mo or W.

11. The method for producing a porous electrode according to any one of claims 1 to 9, wherein the electrode active material P is selected from the group (D) of the following: Li4Ti5O 12 Li4Ti 5-x M x O 12 Where M = V, Zr, Hf, Nb, Ta and 0 ≤ x ≤ 0.25; Niobium oxides and mixed oxides of niobium with titanium, germanium, cerium or tungsten, preferably selected from the group consisting of: Nb2O 5±δ Nb 12 WO 33±δ Nb 14 W3O 44±δ Nb 18 W 16 O 93±δ Nb 16 W5O 55±δ , in which 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 M 1 and M 2 Each of the following 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, M 1 and M 2 They can be the same 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 Ti 1-2x Nb 2+x O 7±δ , where M is an element with an oxidation value of +III. More particularly, M is at least one element selected from the group consisting of Fe, Ga, Mo, Al, and B 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 Ti 2-2x Nb 10+x O 29±δ where M is an element with an oxidation value of +III, more particularly, M is at least one element selected from the group consisting of Fe, Ga, Mo, Al, B and wherein 0 < x ≤ 0.40 and -0.3 ≤ δ ≤ 0.3; 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 Each of the following 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. - M 1 and M 2 They can be the same as or different from each other. - M 3 It is at least one halogen. - 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 M 3 It is at least one halogen, preferably selected from F, Cl, Br, I or a mixture thereof, and 0 ≤ z ≤ 0.3 and 0 ≤ w ≤ 5; 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 For 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 and 0≤x≤1 and 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 ,where - M 1 and M 2 Each of the following 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, Ce, and Sn. - M 1 and M 2 They can be the same as or different from each other. - where 0≤w≤5, 0≤x≤1, 0≤y≤2, and z≤0.3; TiO2; TiO x N y , where x < 2 and 0 <y<0.2; LiSiTON, a tin and silicon-based oxide, and more specifically SiSn formulation 0.87 O 1.20 N 1.72 and its lithiation forms; Nitrogen compounds and MO x N y Type oxynitride, wherein M is at least one element selected from the following: Ge, Si, Sn, Zn, Co, Ni, Cu, Fe or one or more of these elements, wherein x ≥ 0 and y ≥ 0.3; Li 3-X M x N, where M is at least one element selected from Cu, Ni, Co, or a mixture of one or more of these elements and 0 ≤ x ≤ 1; Li 3-X M x N, where M is cobalt (Co) and 0 ≤ x ≤ 0.5; Li 3-X M x N, where M is nickel (Ni) and 0 ≤ x ≤ 0.6; Li 3- X M x N, where M is copper (Cu) and 0 ≤ x ≤ 0.3; Lithium-ionized iron phosphate with the typical molecular formula LiFePO4; A mixed silicon-tin-oxygen-nitride having the typical molecular formula Si a Sn b O y N z where a > 0, b > 0, a + b ≤ 2, 0 < y ≤ 4, 0 < z ≤ 3, also known as SiTON, in particular SiSn 0.87 O 1.2 N 1.72 ; and an oxynitride carbide having the typical molecular formula Si a Sn b C c O y N z where a > 0, b > 0, a + b ≤ 2, 0 < c < 10, 0 < y < 24, 0 < z < 17; Si x N y Type nitrides, particularly where x = 3 and y = 4; Sn x N y In particular, where x = 3 and y = 4, Zn x N y In particular, where x = 3 and y = 2; Li 3-x M x N, where for M=Co, 0≤x≤0.5, for M=Ni, 0≤x≤0.6, and for M=Cu, 0≤x≤0.3; Si 3-x M x N4, where M = Co or Fe and 0 ≤ x ≤ 3. Oxides SnO2, SnO, Li2SnO3, SnSiO3, Li x SiO y Where x>=0 and 2>y>0, Li4Ti5O 12 TiNb2O7, Co3O4, SnB 0.6 P 0.4 O 2.9 and TiO2, Si, Sn, SiO2, SnO2, SiN, SnN and their mixtures The composite oxide TiNb₂O₇ contains 0% to 10% carbon, preferably selected from graphene and carbon nanotubes. Or choose from the following groups (E): - Alloys based on Si, Ge, Sn, Sb, Bi, or P, and alloys of these different compounds. - Maicoenes are a class of two-dimensional materials with a stoichiometry of M. n+1 X n T x Type, wherein M is a transition metal, preferably selected from Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, W, and X is selected from C and / or N, and the surface terminator T is selected from F, Cl, I, Br, O, S, Se, Te, OH, NH2, 1≤n≤4 -Convert anode materials, for example ○G2Ti3O7, G4Ti5O 12、 GTi2(PO4)3 type oxide, where G is Na or K. ○ The oxides, sulfides, selenides, and phosphides of the following elements and their alloys: Si, Ge, Sn, Sb, Bi.

12. A porous electrode that can be obtained by the method according to any one of claims 1 to 11.

13. A method for manufacturing a porous electrode using any one of claims 1 to 11 or a method for manufacturing an energy storage device or a production device using a porous electrode according to claim 12.

14. The method according to claim 13, characterized in that, The energy storage device or energy production device is selected from the group consisting of: capacitors, supercapacitors, hybrid supercapacitors, such as lithium-ion hybrid supercapacitors, sodium-ion hybrid supercapacitors, potassium-ion hybrid supercapacitors, photovoltaic cells, photoelectrochemical cells, or batteries such as lithium-ion batteries, sodium-ion batteries, or potassium-ion batteries.

15. The method of claim 14, wherein the apparatus is a lithium-ion battery, and the method of preparing a porous electrode according to claim 10 is implemented to produce a cathode using an electrode active material P selected from group (A), or the method of claim 11 is implemented to produce an anode using an electrode active material P selected from group (D).

16. The method of claim 14, wherein the apparatus is a sodium-ion battery, and the method of preparing a porous electrode according to claim 10 is implemented to produce a cathode using an electrode active material P selected from group (B), or the method of claim 11 is implemented to produce an anode using an electrode active material P selected from group (E).

17. The method of claim 14, wherein the device is a potassium-ion battery, and the method of preparing a porous electrode according to claim 10 is implemented to produce a cathode using an electrode active material P selected from group (C), or the method of claim 11 is implemented to produce an anode using an electrode active material P selected from group (E).

18. The method according to any one of claims 13 to 17, wherein the device is a lithium-ion battery, a sodium-ion battery, or a potassium-ion battery, and the porous electrode is impregnated with an electrolyte, preferably with a phase carrying lithium ions, sodium ions, or potassium ions, wherein the electrolyte is selected from the group consisting of: - An electrolyte consisting of at least one aprotic solvent and at least one lithium, sodium, or potassium salt; - An electrolyte consisting of at least one ionic liquid and at least one lithium, sodium, or potassium salt; - A mixture of at least one aprotic solvent, at least one ionic liquid, and at least one lithium, sodium, or potassium salt; - An ionic liquid polymer; - A polymeric ionic conductor made by adding at least one lithium, sodium, or potassium salt; and - A polymeric ionic conductor made by adding a liquid electrolyte to a polymeric phase or porous structure of a porous electrode, or by using an ionic conductor polymer, preferably selected from polyethylene oxide (PEO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(propylene carbonate) (PPC), poly(carbonate) (PEC), poly(ethylene carbonate) (PVC), polyvinylidene fluoride (PVDF), polypropylene glycol (PPG), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polydimethylsiloxane (PDMS), poly(ε-caprolactone) (PCL), and poly(trimethylene carbonate) (PTMC).

19. An energy storage device or an energy generation device that can be obtained by the method according to any one of claims 13 to 18.

20. The energy storage device or energy production device according to claim 19, characterized in that... These include capacitors, supercapacitors, hybrid supercapacitors such as lithium-ion hybrid supercapacitors, sodium-ion hybrid supercapacitors, potassium-ion hybrid ultra-large capacitors, photovoltaic cells, photoelectrochemical cells, or batteries such as lithium-ion batteries, sodium-ion batteries, or potassium-ion batteries.

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