Method for manufacturing a porous electrode, and a battery containing the electrode.

Abstract

The present invention relates to a porous electrode usable in electrical energy storage or manufacturing devices such as lithium-ion batteries. This porous electrode is a porous layer comprising at least one electrode active material P and an oxide electron conductor material.

Description

[Technical Field]

[0001] The present invention relates to devices for storing or generating energy. More precisely, it relates to electrodes usable in energy storage or generation devices such as capacitors, photovoltaic cells, or ion-insertion batteries, specifically lithium-ion batteries, sodium-ion batteries, or potassium-ion batteries. The present invention applies to negative and positive electrodes. It relates to porous electrodes that can be impregnated with an ion-conducting phase, such as a solid electrolyte, without using a liquid phase or liquid electrolyte.

[0002] The present invention also relates to a method for producing such porous electrodes using nanoparticles of electrode material and aggregates or aggregates of at least one oxide electron conductor material precursor, and electrodes obtained thereby. The present invention further relates to a method for producing an energy storage or generation device, in particular a method for producing a lithium-ion battery comprising at least one of these electrodes, and batteries obtained thereby. [Background technology]

[0003] Among the various commercially available electrochemical energy storage technologies, lithium-ion batteries have the highest energy density. The electrode structures and chemical compositions that can be used to manufacture these batteries vary. Methods for manufacturing lithium-ion batteries have been reported in numerous papers and patents, and a review article is included in Non-Patent Literature 1, a book published in 2002.

[0004] There is a growing demand for extremely small rechargeable batteries that can be integrated onto electronic circuit boards. These electronic circuits can be used in many fields, such as cards for ensuring transaction security, electronic tags, implantable medical devices, and various micromechanical systems.

[0005] In particular, there is a growing demand for high-capacity rechargeable batteries for supplying power to transportation equipment (electric bicycles, scooters, electric motorcycles, electric vehicles, electric commercial vehicles), as well as for power storage applications such as storing electricity generated by intermittent power generation facilities (wind turbines, solar panels), or stabilizing power grids with volatile supply and demand.

[0006] Furthermore, there is a growing demand for medium-sized rechargeable batteries for various autonomous and portable devices (e.g., mobile phones, portable computers, portable power tools, and kitchen appliances used intermittently).

[0007] In all of these usage scenarios, the ability to rapidly charge the battery is a highly desirable feature. Similarly, these batteries must not be at risk of thermal runaway. Ultimately, it is desirable that they be able to operate over a wide temperature range.

[0008] According to prior art, electrodes for lithium-ion batteries can be manufactured using coating techniques, particularly by coating. These methods allow for the deposition of an ink consisting of powdered active material particles onto the surface of a substrate, with the average particle size of the particles constituting this powder typically ranging from 5 μm to 15 μm in diameter.

[0009] These deposition techniques, particularly coatings, allow for the fabrication of layers with thicknesses ranging from approximately 20 μm to 400 μm. The power and energy of a battery can be controlled by adjusting the layer thickness and porosity, the size of the active particles that comprise it, and the various components present within the layer, such as binders or conductive materials. To manufacture microbatteries, it is desirable to reduce the thickness of each layer that makes up the microbattery.

[0010] To obtain low-cost, high-performance electrodes, it is necessary to keep in mind that, in addition to the problems associated with ink formulation, the ratio of the electrode's energy density to its power density can be adjusted by the size of the active material particles, and indirectly by the specific surface area and thickness of the electrode layer. Non-patent document 2 shows the effects of electrode thickness and its porosity on discharge characteristics (power) and energy density, respectively.

[0011] Binder-free mesoporous electrode layers for lithium-ion batteries can be deposited by electrophoresis, as is known from Patent Document 1 (I-TEN). Although these electrode layers can be impregnated with liquid electrolytes, their electrical resistivity remains quite high.

[0012] Especially when electrodes are thick or manufactured from electrode active materials with low electrical conductivity, a certain amount of electron-conducting material, such as carbon black, is generally added to the electrode active material particles to improve the low electrical conductivity of the electrodes. Ideally, the electron-conducting particles should be present at any location on the surface of the electrode active material particles, allowing for simultaneous insertion / deinsertion across the entire surface of the electrode active material particles. This maximizes the current density and minimizes stress and localized heating due to non-uniform electron transport.

[0013] In practice, controlling the placement of carbon black within electrodes is extremely difficult. Furthermore, these problems are becoming increasingly severe with the increasing use of smaller particle active materials. Non-uniform distribution of carbon black within electrodes significantly increases electrode polarization, leading to increased series resistance in batteries containing such electrodes. Local imbalances in charge states become more pronounced as current density increases. These imbalances result in reduced cycle performance, safety risks, and power limitations in battery cells. The same applies when the porosity of the electrodes is non-uniform, i.e., the sizes are dispersed, and this non-uniformity contributes to making wetting of the electrode pores more difficult.

[0014] Under these circumstances, in order to reduce the electrical resistivity of the electrode, the applicant has developed a mesoporous electrode comprising a mesoporous layer made of at least one type of electrode active material and a mesoporous layer of at least one type of electrode active material having a carbon coating on and within the pores of the mesoporous layer. This is known from Patent Document 2 (I-TEN). While the presence of this carbon electrical conductor coating on the electrode can reduce the electrical resistivity of the electrode, it does not significantly improve voltage, temperature, and electrochemical stability. Furthermore, forming a carbon electrical conductor coating on the electrode is costly and difficult to implement. [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] International Publication No. 2019 / 215407 [Patent Document 2] International Publication No. 2021 / 220174 [Non-patent literature]

[0016] [Non-Patent Document 1] Advances in Lithium-Ion Batteries (editors: W. van Schalkwijk, B. Scrosati, Kluever Academic / Plenum Publishers) [Non-Patent Document 2] J. Newman ("Optimization of Porosity and Thickness of a Battery Electrode by Means of A Reaction-Zone Model", J. Electrochem. Soc., 142 (1), p. 97-101 (1995)) [Overview of the project]

[0017] As the demand for ultra-miniature rechargeable batteries increases, electrodes must meet increasingly stringent specifications. Electrodes must possess high chemical and electrochemical stability, robustness, and corrosion resistance, thereby providing batteries with high cycle characteristics, storage stability, temperature stability, and long-term reliability, enabling both high energy density and high power density. This invention aims to improve upon at least some of the shortcomings of the prior art described above.

[0018] More precisely, the problem that the present invention aims to solve is to provide a method for manufacturing a porous electrode that has uniform and high electronic conductivity, a controlled pore density, and is simple, safe, quick, easy, and inexpensive to implement.

[0019] Furthermore, the present invention aims to provide a safe porous electrode that has high electronic conductivity, a stable mechanical structure, good temperature stability, particularly good thermal stability at high temperatures, and a long service life, regardless of the electrode thickness.

[0020] Another object of the present invention is to provide a battery electrode that can operate at high temperatures without reliability issues and fire hazards.

[0021] Another object of the present invention is to provide a porous electrode that, in addition to the features described above, can be readily wetted and impregnated with an ionic liquid or polymer.

[0022] Another object of the present invention is to provide a method for manufacturing an energy storage or generation device comprising a porous electrode according to the present invention, such as a capacitor, supercapacitor, hybrid supercapacitor, photocell, photochemical cell or battery, in particular a lithium-ion battery, sodium-ion battery, or even a potassium-ion battery.

[0023] Another object of the present invention is to provide energy storage or generation devices such as batteries, particularly lithium-ion batteries and microbatteries, capacitors, supercapacitors, lithium-ion supercapacitors (hereinafter referred to as LiC), sodium-ion hybrid supercapacitors (hereinafter referred to as SIHC), potassium-ion hybrid supercapacitors (hereinafter referred to as PIHC), and other hybrid supercapacitors that can store high energy density, recover this energy at very high power density (especially within capacitors or supercapacitors), withstand high temperatures, have excellent cycle life, and have improved safety.

[0024] (Purpose of the present invention) To improve the performance of electrodes usable in energy storage or production equipment, particularly in conventional lithium-ion batteries, and especially to significantly improve voltage, temperature, and electrochemical stability while reducing electrical resistivity, the inventors sought alternatives to the carbon conductive coatings described in International Publication No. 2021 / 220174 (I-TEN).

[0025] According to the present invention, the 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 having a porosity of 25% to 60% by volume. The electrode according to the present invention comprises at least one electrode active material and an oxide electron conductor material, and is a porous layer, preferably a mesoporous layer, having a porosity of 25% to 60% by volume. Advantageously, the electrode according to the present invention comprises a region of electrode active material P covered at least partially with a coating of oxide electron conductor material throughout the entire internal volume of the electrode and on the surface, preferably the electrode according to the present invention comprises a region of electrode active material P covered with a coating of oxide electron conductor material throughout the entire internal volume of the electrode and on the surface.

[0026] This completely solid, porous, preferably mesoporous, organic-free layer is obtained from aggregates and / or aggregates of primary nanoparticles consisting of at least one electrode active material and at least one oxide electron conductor material precursor. The size of the primary particles constituting these aggregates and / or aggregates is on the order of nanometers or tens of nanometers, and the aggregates and / or aggregates contain at least four primary particles.

[0027] In the first embodiment, the substrate is a substrate capable of functioning as a current collector, or in the second embodiment, it is a temporary intermediate substrate, which will be described in more detail below.

[0028] The thickness of the deposited layer can be increased by using aggregates with diameters of tens or hundreds of nanometers, rather than non-aggregated primary particles of about 1 nanometer or 10 nanometers. However, in order to form a continuous mesoporous film during the heat treatment of the layer, the aggregates must remain small. If there are two or more aggregates that are large, sintering is inhibited, and two different types of porosity are formed within the layer: porosity between the aggregates and porosity within the aggregates.

[0029] After sintering, a porous, preferably mesoporous, layer or plate is obtained without the use of carbon black or an organic binder, in which all primary nanoparticles are welded to each other (by the necking phenomenon, which is otherwise known), forming a continuous mesoporous network characterized by unimodal porosity. The porous layer, preferably mesoporous layer, thus obtained is completely solid and ceramic. There is no risk of loss of electrical contact between active material particles during cycling, improving the battery's cycle characteristics. Furthermore, after sintering, the porous layer, preferably mesoporous layer, adheres completely to the metal substrate to which it is deposited or transferred (if initially deposited on an intermediate substrate).

[0030] Heat treatment is performed at high temperatures to sinter the nanoparticles, completely drying the electrodes and removing any traces 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), low-temperature heat treatment (de-binding) can be performed to dry the placed or deposited electrodes and remove any traces of water, solvents, or other organic additives (stabilizers, binders) adsorbed on the surface of the active material particles. This de-binding can be performed in an oxidizing atmosphere.

[0031] The final electrode porosity can be adjusted depending on the sintering time and temperature. The porosity can be adjusted within a range of 25% to 60% depending on the required energy density.

[0032] In any case, the power density of the electrodes obtained in this way remains extremely high due to their porosity, preferably especially due to their mesoporosity. Furthermore, regardless of the size of the mesopores in the active material (it should be understood that the concept of nanoparticles no longer applies to materials that have a three-dimensional structure with a network of channels and mesopores after sintering), the dynamic equilibrium of the cell is perfectly maintained, which contributes to maximizing the power density and lifespan of the battery cell.

[0033] The electrode according to the present invention has a high specific surface area, thereby reducing the ionic resistance of the electrode. However, in order for this electrode to supply maximum power, it still needs to have very good electronic conductivity to avoid resistance losses in the battery. Improving the electronic conductivity of the cell becomes more important as the thickness of the electrode increases. Furthermore, this electronic conductivity must be perfectly uniform throughout the electrode to avoid localized areas of high electrical resistance that could lead to the formation of hot spots during the battery's power operation.

[0034] According to the essential features of the present invention, the electrode according to the present invention comprises at least one electrode active material and an oxide electron conductor material, preferably comprising a region of electrode active material P covered at least partially with a coating of the oxide electron conductor material throughout the entire internal volume and on the surface of the electrode, and preferably comprising a region of electrode active material P completely dispersed throughout the entire internal volume and on the surface of the electrode and covered with a coating of the electron conductor material.

[0035] The oxide electrically conductive material coating according to the present invention is preferably composed of SnO2, aluminum-doped ZnO (ZnO:Al, preferably with a molar ratio of Zn:Al of 1:0.015 to 1:0.05), MoO3, SrMoO3, In2O3, Ga2O3, or indium tin oxide.

[0036] The thickness of the oxide electron conductor material coating over 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 electron conductor material can be manufactured from at least one precursor of the oxide electron conductor material, particularly from at least one liquid precursor of the oxide electron conductor material.

[0037] This thickness is measured using appropriate techniques, specifically by a transmission microscope.

[0038] More specifically, as described above, the method according to the present invention must include a step of forming a layer from aggregated nanoparticles of electrode material (active material) and a precursor of at least one oxide electron conductor material, thereby naturally "welding" the nanoparticles and, after solidification treatment such as annealing, generating a porous and rigid three-dimensional structure without the use of an organic binder. This porous layer, preferably a mesoporous layer, is perfectly suited to surface treatment by gaseous or liquid means, or by impregnation that penetrates deep into the open porous structure of the layer.

[0039] A first object of the present invention is a method for manufacturing a porous electrode, particularly a method for manufacturing a porous electrode for an electrical energy storage or generation device such as a battery, wherein the electrode is a porous layer provided on a substrate containing at least one electrode active material P and an oxide conductive material, the electrode does not contain a binder, has a porosity of 25% to 60% by volume, preferably 25% to 50% by volume, and has pores with an average diameter of less than 100 nm, and the manufacturing method comprises the following steps: (a) A step of providing a colloidal suspension or paste comprising an aggregate or aggregate consisting of a substrate, a precursor of at least one oxide conductive material, and primary nanoparticles of at least one electrode active material P, wherein the primary mean diameter D of the primary nanoparticles 50 The midrange is 2nm to 400nm, preferably 2nm to 100nm, more preferably 2nm to 60nm, and the aggregate or aggregate mass has a median diameter D of 50nm to 900nm, preferably 100nm to 800nm. 50 The process is understood to include the fact that the substrate can be a substrate or intermediate substrate capable of functioning as a current collector. (b) A step of mixing one or more oxide conductive material precursors with the colloidal suspension or paste containing aggregates or aggregates of primary nanoparticles of at least one electrode active material P provided in step (a) to form a mixture, (c) A step of forming a layer 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, and coating, preferably doctor blade coating, roll coating, curtain coating, dip coating, or slot die coating. (d) A step of drying the layer obtained in step (c) to obtain a dried layer, wherein, if necessary, after drying step (d), a step of separating the dried layer from the intermediate substrate. (e) A step of converting one or more precursors of oxide conductive materials into oxide conductive materials so that the dry layer contains the oxide conductive material, (f) A step of solidifying the layer 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 during the same heat treatment. Includes.

[0040] The method according to the present invention may include heat treatment of the dried layer in step (e), in step (f), or between step (e) and step (f), preferably in an oxidizing atmosphere.

[0041] Advantageously, after step (f), the pores of the porous electrode are impregnated with an electrolyte. Depending on the intended type of battery, the electrolyte may include a lithium salt, a potassium salt, or a sodium salt. Preferably, the electrolyte is - An electrolyte comprising at least one aprotic solvent and at least one lithium salt, sodium salt, or potassium salt; - An electrolyte comprising 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 salt, sodium salt, or potassium salt; - Ionic liquid polymer; - A polymer made ionically conductive by the addition of at least one of the following: lithium salt, sodium salt, or potassium salt; - A polymer made into an ion conductor by adding a liquid electrolyte to either the polymer phase or the porous structure of the porous electrode, or by an ion-conducting polymer, preferably an ion-conducting polymer 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); This is a phase supporting lithium ions, sodium ions, or potassium ions selected from the group consisting of the following.

[0042] The lithium ion-supporting phase may include a mixture of several ionic liquids. Advantageously, the ionic liquids may include 1-ethyl-3-methylimidazolium (also known as EMI+) and / or n-propyl-n-methylpyrrolidinium (PYR+). 13 + (also known as n-butyl-n-methylpyrrolidinium (PYR) 14 + A type of cation also known as ) and bis(trifluoromethanesulfonyl)imide (TFSI - ) and / or bis(fluorosulfonyl)imide (FSI -It can be combined with anions of the ) type. To form an electrolyte, a lithium salt such as LiTFSI can be dissolved in an ionic liquid that acts as a solvent, or in a solvent such as γ-butyrolactone. γ-butyrolactone prevents crystallization of the ionic liquid and provides a wider operating temperature range, especially at low temperatures. The phase supporting sodium or potassium ions may consist of a mixture of several ionic liquids. The ionic liquids are as described above. To form an electrolyte, sodium salts such as NaTFSI can be used instead of LiTFSI in sodium-ion batteries, and potassium salts such as KTFSI can be used instead of LiTFSI in potassium-ion batteries. The phase supporting lithium, sodium, or potassium ions may consist of an ionic liquid polymer such as poly(1-vinyl-3-alkylimidazolium) or poly(1-vinyl-N-alkylpyrrolidinium).

[0043] In step (c), layers can be formed on one or both sides of the substrate.

[0044] Advantageously, if the substrate is an intermediate substrate, the layers of the intermediate substrate are separated in step (d) after drying, particularly after solidification, to form a porous plate.

[0045] Advantageously, if the substrate is an intermediate substrate, after step (f), an electronic conductor sheet is prepared in which at least one side, or both sides, are covered with a thin film of conductive adhesive, and then at least one porous plate is bonded to one side, preferably both sides, of the conductive sheet to form a plate or porous layer, preferably a mesoporous layer, on a substrate capable of functioning as a current collector. In this application, the terms “porous layer” and “porous plate” are used interchangeably.

[0046] Advantageously, step (b) is carried out by contacting a colloidal suspension or paste containing aggregates or agglomerates of primary nanoparticles of at least one electrode active material P prepared in step (a) with a liquid phase containing a precursor of at least one of the oxide electron conductor materials, and the conversion of the precursor of the one or more oxide electron conductor materials to the oxide electron conductor material is preferably carried out by a heat treatment such as calcination carried out in air or an oxidizing atmosphere.

[0047] Advantageously, the precursor of the one or more oxide electron conductor materials is selected from organic salts containing one or more metal elements capable of forming an oxide electric conductor after a heat treatment such as calcination, and the conversion to the electron conductor material is preferably a heat treatment such as calcination carried out in air or an oxidizing atmosphere.

[0048] These organic salts are preferably the following - an alcoholate of at least one metal element capable of forming an oxide electric conductor after a heat treatment such as calcination preferably carried out in air or an oxidizing atmosphere, - a nitrate of at least one metal element capable of forming an oxide electric conductor after a heat treatment such as calcination preferably carried out in air or an oxidizing atmosphere, - an oxalate of at least one metal element capable of forming an oxide electric conductor after a heat treatment such as calcination preferably carried out in air or an oxidizing atmosphere, - an acetate of at least one metal element capable of forming an oxide electric conductor after a heat treatment such as calcination preferably carried out in air or an oxidizing atmosphere, - and / or preferably, the metal element is tin, zinc, indium, gallium, molybdenum, or a mixture of two, three, four, or five of these elements, selected from.

[0049] The metal element can contain at least one dopant element.

[0050] Advantageously, the porous layer obtained at the end of step (f) is 10 m 2 / g~500m 2 It has a specific surface area between / g and / or a thickness of 2μm to 400μm, preferably 2μm to 300μm, more preferably 3μm to 200μm.

[0051] Advantageously, if the substrate is capable of acting as a current collector, the porous electrode obtained at the end of step (f) is 10m 2 / g~500m 2 It has a specific surface area between / g and / or a thickness of 2μm to 20μm.

[0052] Advantageously, when the substrate is an intermediate substrate, the porous electrode obtained at the end of process (f) is 10m 2 / g~500m 2 It has a specific surface area of ​​ / g and / or a thickness of 25μm to 500μm, preferably 50μm to 400μm.

[0053] Advantageously, if 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 porous plate obtained at the end of step (d) is subjected to heat treatment, preferably in an oxidizing atmosphere, and it is understood that this heat treatment and steps (e) and / or (f) can be performed in the same heat treatment process.

[0054] Advantageously, the electrode active material P is -Oxide LiMn2O4, Li 1+x Mn 2-x O4(0 <x<0.15である)、LiCoO2、LiNiO2、LiMn 1.5 Ni 0.5 O4, LiMn 1.5 Ni 0.5-x X x O4 (Here, X is selected from Al, Fe, Cr, Co, Rh, Nd, and other rare earth elements (e.g., Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), 0 <x<0.1である。)、LiMn 2-x M x O4(M=Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg, or a mixture thereof, 0 <x<0.4である。)、LiFeO2、LiMn 1 / 3 Ni 1 / 3 Co 1 / 3 O2, LiLiLi 0.8 Co 0.15 Al 0.05 O2, Lial x Mn 2-x O4 (Here, 0 <x<0.15である。)、LiNi 1 / x Co 1 / y Mn 1 / z O2(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 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 0.6 <x<1、0<y<0.5、0.25≦z<1、A≠MeおよびA≠Nb、および0≦p≦0.20である。) -Li x Nb y-a N a M z-b P b O 2-c F c(Here, 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 M, N, and P are each one or more elements 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 (Here, 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 (M = Fe, Co, Ni or a mixture of different elements thereof), LiMPO4F (M = V, Fe, T or a mixture of different elements thereof); Phosphates of the formula LiMM’PO4 (where M and M’ (M ≠ M’) are selected from Fe, Mn, Ni, Co, V, for example, LiFe x Co 1-xPO4 (where 0 < x < 1); -Fe 0.9 Co 0.1 OF; FeF3; LiMSO4F (M = Fe, Co, Ni, Mn, Zn, Mg); - Titanium oxysulfide (TiO y S z , z = 2 - y and 0.3 ≦ y ≦ 1), Tungsten oxysulfide (WO y S z , 0.6 < y < 3 and 0.1 < z < 2), CuS, CuS2, Li x V2O5 (0 < x ≦ 2), Li x V3O8 (0 < x ≦ 1.7), Li x TiS2 (0 < x ≦ 1), Lithium - titanium oxysulfide (Li x TiO y S z , z = 2 - y, 0.3 ≦ y ≦ 1 and 0 < x ≦ 1), Li x WO y S z (z = 2 - y, 0.3 ≦ y ≦ 1 and 0 < x ≦ 1), Li x CuS (0 < x ≦ 1), Li x CuS2 (0 < x ≦ 1); selected from the group (A) consisting of, or - Transition metal oxides: · Na<00​​​​​​​​​​​​​​​​​​​​​​​2+z (u + v + w = 3 and M, M’, M’’ are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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 (0.67 ≤ x ≤ 1.0; 0.5 ≤ y ≤ 0.7 and 0.1 ≤ z ≤ 0.3); - Prussian blue and / or Prussian blue analogs, known as the abbreviation PBA: · Na which is a transition metal or a transition metal alloy 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, and the transition metal and the transition metal alloy are selected from Fe, Ni, Co and Mn, 0 ≤ x ≤ 2; y ≤ 1 and 0 ≤ n ≤ 12); - Polyoxyanion compounds: · Na x M2(XO4)3 (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W), for example Na3V2(PO4)3; · Na x M3(XO4)2(X2O7) (for 0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); · Na x M(X2O7) (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); · Na x M2(XO4)2F3 (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); · Na x M2(XO4)2F 3-y O y(0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, 0.07 ≤ y ≤ 0.12 and X = P, S, As, Si, Mo or W); ·Na x M2O2(XO4)2F (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); ·Na x MXO4(0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); belonging to group (B) consisting of: - Transition metal oxides: ·K x MO 2+z (M is selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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 (u + v = 2 and M, M’ are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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 (u + v + w = 3 and M, M’, M’’ are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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<​​​​​​​​​​​​​1 [M 2 ’(CN)6] y .nH2O(M 1 is a transition metal or a transition metal alloy, and M 2’ is a transition metal or a transition metal alloy, the transition metal and the transition metal alloy are selected from Fe, Ni, Co and Mn, 0 ≦ x ≦ 2; y ≦ 1 and 0 ≦ n ≦ 12); - Poly anion compound: ·K x M2(XO4)3(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)(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)(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(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 (0 < x ≦ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, 0.07 ≦ y ≦ 0.12, and X = P, S, As, Si, Mo or W); ·K x M2O2(XO4)2F(0 < x ≦ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, and X = P, S, As, Si, Mo or W); ·K x MXO4(0 < x ≦ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, and X = P, S, As, Si, Mo or W), belongs to the group (C) consisting of.[[ID=​​​​

[0056] Advantageously, the electrode active material -Li4Ti5O 12 Li4Ti 5-x M x O 12 (M = V, Zr, Hf, Nb, Ta, and 0 ≤ x ≤ 0.25); - Niobium oxide, and mixed oxides of niobium with titanium, germanium, cerium, or tungsten, preferably, • 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 (0≦δ≦2), LiNbO3, -TiNb2O 7±δ Li w TiNb2O7(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 [Here, M 1 and M 2 Each of these is at least one 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 These can be identical or different from each other, and 0≦w≦5, 0≦x≦1, 0≦y≦2, and 0≦δ≦0.3. ·La x Ti 1-2x Nb 2+x O7[Here, 0 <x<0.5である。]; ·Mx Ti 1-2x Nb 2+x O 7±δ [Here, M is an element with an oxidation value of +III, and more specifically, M is at least one element selected from the group consisting of Fe, Ga, Mo, Al, and B, 0 <x≦0.20および-0.3≦δ≦0.3である。];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 [Here, M is an element with an oxidation value of +III, and more specifically, M is at least one element selected from the group consisting of Fe, Ga, Mo, Al, and B, 0 <x≦0.40および-0.3≦δ≦0.3である。]; 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 [Here, M 1 and M 2 Each of these 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 may be the same or different from each other. M 3 is at least one type of halogen, Here, 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 [Here, M 3 [1] is at least one halogen, preferably selected from F, Cl, Br, or I, or a mixture thereof, with 0 ≤ z ≤ 0.3 and 0 ≤ w ≤ 5; Ti 1-x Ge x Nb 2-y M 1 y O 7±z Li w Ti 1-x Ge x Nb 2-y M 1 y O 7±z 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 [Here, M 1 is at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, and Sn; 0≦w≦5, 0≦x≦1, 0≦y≦2, and z≦0.3. Ti 1-x Ge x Nb 2-y M 1 y O 7-z M 2 z Li w Ti 1-x Ge x Nb2-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 [Here, M 1 and M 2 Each of these 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 may be the same or different from each other. Here, 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2, and z ≤ 0.3. Selected from the group consisting of; -TiO2;TiO x N y (x<2 and 0 <y<0.2); -LiSiTON, a tin-silicon oxynitride, more specifically, by the formula SiSn 0.87 O 1.20 N 1.72 , and its lithium-ionized form; -MO x N y Nitrides and oxynitrides of type [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, x≧0 and y≧0.3]; -Li 3-X M xN (M is at least one element selected from Cu, Ni, Co, or a mixture composed of one or more of these elements, and 0 ≦ x ≦ 1.) -Li 3-X M x N (M is cobalt (Co), and 0 ≦ x ≦ 0.5); Li 3-X M x N (M is nickel (Ni), and 0 ≦ x ≦ 0.6), Li 3-X M x N (M is copper (Cu), and 0 ≦ x ≦ 0.3); - Lithium iron phosphate (generally represented by the formula LiFePO4); - Typically Si a Sn b O y N z A silicon and tin mixed oxynitride represented by (a > 0, b > 0, a + b ≦ 2, 0 < y ≦ 4, 0 < z ≦ 3), also called SiTON, especially SiSn 0.87 O 1.2 N 1.72 ; Also, a typical formula Si a Sn b C c O y Nz (a > 0, b > 0, a + b ≦ 2, 0 < c < 10, 0 < y < 24, 0 < z < 17) oxynitride carbide; - Si x N y Type nitride (especially x = 3 and y = 4), Sn x N y Type nitride (especially x = 3 and y = 4), Zn x N y Type nitride (especially x = 3 and y = 2); Li 3-x M x N-type nitride (when M = Co, 0 ≦ x ≦ 0.5; when M = Ni, 0 ≦ x ≦ 0.6; when M = Cu, 0 ≦ x ≦ 0.3); Si 3-x M x N4 (M = Co or Fe, and 0 ≦ x ≦ 3), - Oxides such as SnO2, SnO, Li2SnO, SnSiO, Li x SiO y (x >= 0 and 2 > y > 0), Li4Ti5O 12TiNb2O7, Co3O4, SnB 0.6 P 0.4 O 2.9 and TiO2; -Si, Sn, SiO2, SnO2, SiN, SnN, and mixtures thereof; - A TiNb2O7 composite oxide containing 0% to 10% by mass of carbon, wherein the carbon is preferably selected from graphene and carbon nanotubes; Selected from group (D) consisting of, or - Alloys based on Si, Ge, Sn, Sb, Bi, and P, and alloys of various compounds thereof. -MXenes. MXenes is M n+1 X n T x A class of two-dimensional materials with a stoichiometry of type 1, where M is a transition metal, preferably selected from Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, and W. X is selected from C and / or N, and T is a surface termination selected from F, Cl, I, Br, O, S, Se, Te, OH, and NH2, where 1 ≤ n ≤ 4. - Conversion type negative electrode material, for example G2Ti3O 7、 G4Ti5O 12、 Oxides of GTi2(PO4)3 (where G is Na or K), The following elements Si, Ge, Sn, Sb, Bi and their alloys, oxides, sulfides, selenides, phosphides, It belongs to group (E), which consists of the following.

[0057] Advantageously, the electrode active material P mentioned above is used to manufacture the negative electrode.

[0058] Another object of the present invention is a porous electrode, particularly for electrical energy storage or generation devices, comprising at least one electrode active material P and an oxide electron conductor material, without a binder, and having a porosity of 25% to 60% by volume, preferably 25% to 50%.

[0059] Another object of the present invention is a porous electrode that can be obtained by the method of the present invention. Another object of the present invention is a porous electrode that can be obtained by the method of the present invention, comprising at least one electrode active material P and an oxide electron conductor material, without a binder, and having a porosity of 25% to 60% by volume, preferably 25% to 50%.

[0060] Another object of the present invention is a method for manufacturing an electrical energy storage or generation device, preferably selected from the group consisting of capacitors, supercapacitors, hybrid supercapacitors such as lithium-ion hybrid supercapacitors, sodium-ion hybrid supercapacitors, and potassium-ion hybrid supercapacitors, photovoltaic cells, photoelectrochemical cells, and batteries such as lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries, by carrying out the manufacturing method of porous electrodes according to the present invention or by using the porous electrodes according to the present invention. Another object of the present invention is a method for manufacturing an electrical energy storage or generation device such as batteries, capacitors, supercapacitors, hybrid supercapacitors such as lithium-ion hybrid supercapacitors, sodium-ion hybrid supercapacitors, and potassium-ion hybrid supercapacitors, photochemical cells, and photovoltaic cells, and in particular a method for manufacturing a lithium-ion battery, sodium-ion battery, or potassium-ion battery by carrying out the manufacturing method of porous electrodes according to the present invention.

[0061] Advantageously, if the electrical energy storage or generation device is a lithium-ion hybrid supercapacitor or lithium-ion battery, the method for manufacturing the positive electrode uses the electrode active material P selected from group (A), and the method for manufacturing the negative electrode uses the electrode active material P selected from group (D).

[0062] Advantageously, if the electrical energy storage or generation device is a sodium-ion hybrid supercapacitor or sodium-ion battery, the method for manufacturing the positive electrode uses an electrode active material P selected from group (B), and the method for manufacturing the negative electrode uses an electrode active material P selected from group (E) (where G is sodium, appropriate).

[0063] Advantageously, if the electrical energy storage or generation device is a potassium-ion hybrid supercapacitor or potassium-ion battery, the method for manufacturing the positive electrode uses electrode active material P selected from group (C), and the method for manufacturing the negative electrode uses electrode active material P selected from group (E) (where G is K, appropriate).

[0064] Advantageously, in the lithium-ion battery manufacturing method, the porous electrode manufacturing method is carried out to manufacture a positive electrode using an electrode active material P selected from group (A), or to manufacture a negative electrode using an electrode active material P selected from group (D).

[0065] In particular, this method is suitable for the manufacture of batteries, and generally, batteries according to the present invention can be designed and sized as surface mount components (surface mount technology is technically abbreviated as "SMT") and are compatible with microelectronics manufacturing methods, especially robotic methods for filling electronic substrates known by the term "pick and place".

[0066] Advantageously, the porous electrode is preferably, by an electrolyte, - An electrolyte comprising at least one aprotic solvent and at least one lithium salt, sodium salt, or potassium salt; - An electrolyte comprising 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 salt of lithium, sodium, or potassium; - Ionic liquid polymer; - A polymer made into an ion conductor by adding at least one lithium salt, sodium salt, or potassium salt; and - A polymer made into an ion conductor by adding a liquid electrolyte to either the polymer phase or the porous structure of the porous electrode, or by an ion-conducting polymer, preferably an ion-conducting polymer 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); It is impregnated with a phase supporting lithium ions, sodium ions, or potassium ions, selected from the group consisting of the following.

[0067] Another object of the present invention is an electrical energy storage or production apparatus that can be obtained according to the manufacturing method of the present invention, preferably a lithium-ion battery, a sodium-ion battery, or a potassium-ion battery that can be obtained by the manufacturing method according to the present invention.

[0068] Advantageously, the electrical energy storage or generation device according to the present invention is a capacitor, a supercapacitor, such as a lithium-ion hybrid supercapacitor, a sodium-ion hybrid supercapacitor, a potassium-ion hybrid supercapacitor, a photovoltaic cell, a photochemical cell, or a battery such as a lithium-ion battery, a sodium-ion battery, or a potassium-ion battery.

[0069] Advantageously, if the electrical energy storage or generation device is a lithium-ion hybrid supercapacitor or lithium-ion battery, the electrode active material P is selected from group (A) of positive electrode active materials and / or group (D) of negative electrode active materials.

[0070] Advantageously, if the electrical energy storage or generation device is a sodium-ion hybrid supercapacitor or sodium-ion battery, the electrode active material P is selected from group (B) of positive electrode active materials and / or group (E) of negative electrode active materials (where appropriate, G is Na).

[0071] Advantageously, if the electrical energy storage or generation device is a potassium-ion hybrid supercapacitor or potassium-ion battery, the electrode active material P is selected from group (C) of positive electrode active materials and / or group (E) of negative electrode active materials (where G is K, where appropriate).

[0072] The method according to the present invention is particularly suitable for manufacturing porous electrodes having a thickness greater than 1 μm or greater than 3 μm, which ensures a low series resistance of the battery.

[0073] Another object of the present invention is an electrical energy storage or production apparatus such as a battery, capacitor, supercapacitor, photovoltaic cell, or photochemical cell, comprising a porous electrode according to the present invention, or a porous electrode that can be selected by a method according to the present invention. [Modes for carrying out the invention]

[0074] (Detailed description of the invention) 1.Definition This invention relates to a porous electrode in which an accessible surface, i.e., the outer surface of the electrode, and an accessible internal pore are covered with an oxide electron conductor material. The term "oxide electron conductor" includes oxide electron conductors and oxide electron semiconductors.

[0075] In this document, particle size is defined by its maximum dimension. "Nanoparticle" means a nanometer-sized particle or object in which at least one dimension is 400 nm or less.

[0076] An "ionic liquid" is a liquid salt that can transport electricity, and is distinguished from a molten salt, which has a melting point below 100°C. Some of these salts remain liquid at room temperature and do not solidify at very low temperatures. Such salts are called "room temperature ionic liquids."

[0077] The term "electrolyte" refers to a substance that exhibits ionic conductivity due to the presence of mobile ions, and can be liquid or solid without a liquid phase. These ions include Li + na + or K + It is preferable that the electrolyte is in the form of a gel. The electrolyte is an electronic insulator to electrically isolate the electrodes.

[0078] A “mesoporous” material refers to a solid that has pores within its structure that are intermediate in size between micropores (less than 2 nm wide) and macropores (more than 50 nm wide), i.e., pores between 2 nm and 50 nm in size, called “mesopores.” 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, even if the mesopores defined above have dimensions in nanometer units as defined in nanoparticles, the term “nanopores” is not used herein. Those skilled in the art will understand that pores smaller than mesopores are called “micropores.”

[0079] The concept of porosity (and the terminology explained above) is described in detail in the paper "Texture of Powdered or Porous Materials" by F. Rouquerol et al. (Analysis and Characterization, booklet, p. 1050). This paper also describes techniques for characterizing porosity, particularly the BET method.

[0080] In the context of this invention, the term "porous layer" means a layer having pores. "Mesoporous layer" means a layer having mesopores. In these layers, pores and mesopores contribute significantly to the total pore volume, a condition clearly indicated by the expression "porous / mesoporous layer with porosity exceeding X volume%" as used herein.

[0081] The term "aggregate," according to the IUPAC definition, refers to a collection of weakly bound primary particles. In this case, these primary particles, preferably nanoparticles, are particles with a diameter measurable by a transmission electron microscope. Aggregates of aggregated primary nanoparticles can usually be broken down (i.e., reduced to primary nanoparticles) in a suspension in a liquid phase under the action of ultrasound using techniques known to those skilled in the art.

[0082] According to the IUPAC definition, the term "agglomerate" refers to a collection of primary particles or aggregates that are strongly bound together.

[0083] 2. Preparation of nanoparticle suspension The porous electrode according to the present invention is formed from a colloidal suspension or paste of clusters and / or aggregates of nanoparticles.

[0084] In a more preferred embodiment of the present invention, nanoparticles are prepared directly at their primary size by precipitation, pecini synthesis, spray pyrolysis, hydrothermal synthesis, or solvothermal synthesis. Hydrothermal synthesis or solvothermal synthesis can be used to obtain nanoparticles having a very narrow size distribution, preferably known as “monodisperse nanoparticles”. The size of these non-aggregated or non-aggregated clump nanopowder / nanoparticles is called the primary size. The primary size is typically 2 nm to 400 nm, preferably 2 nm to 100 nm, more preferably 2 nm to 60 nm, and advantageously 10 nm to 50 nm, preferably 10 nm to 30 nm. This facilitates the formation of interconnected electron-conducting and ion-conducting mesoporous networks through the “necking” phenomenon in subsequent method steps.

[0085] To facilitate the production of sediments or green sheets, particularly the creation of thick, crack-free sediments, additives such as binders may be added to suspensions of nanoparticles (clusters and / or aggregates of nanoparticles, which are understood to also be in the form of nanoparticles).

[0086] A layer of at least one oxide electron conductor material precursor is formed on preferably monodisperse aggregates and / or aggregates of primary nanoparticles of at least one electrode active material P by any suitable means.

[0087] 3. A mixture comprising a precursor of at least one oxide electronic conductor material and a colloidal suspension or paste containing aggregates and / or aggregates of primary particles of at least one electrode active material P - Formation of a layer of the precursor of at least one oxide electronic conductor material on aggregates and / or aggregates of primary nanoparticles of at least one electrode active material P

[0088] A significant advantage is that the oxide electron conductor material layer can be obtained by a variety of methods and any suitable means, in particular by contacting a colloidal suspension or paste containing aggregates or aggregates of primary nanoparticles of at least one electrode active material P with a liquid phase containing a precursor of at least one oxide electron conductor material, and then converting the precursor of the electron conductor material or one or more electron conductor materials into an electron conductor material.

[0089] More generally, the accessible surface of an aggregate or mass of primary nanoparticles of at least one electrode active material P is covered using the technique for producing a coating of the precursor of at least one oxide electronic conductor material described herein.

[0090] The formation of a layer of precursors of at least one oxide electronic conductor material onto a suspension or paste aggregate and / or aggregate 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 aggregate / aggregate.

[0091] This method can be implemented simply, quickly, and easily. Advantageously, one or more precursors of the electron conductor material are selected from organic salts containing one or more metal elements capable of forming an oxide electron conductor after heat treatment, such as calcination, preferably carried out in air or an oxidizing atmosphere. The oxide electron conductor may optionally contain at least one dopant element. These metal elements, preferably metal cations, are advantageously selected from tin, zinc, indium, gallium, molybdenum, or mixtures of two, three, four, or five of these elements. The organic salt is preferably the following: - Preferably an alkoxide of at least one metallic element capable of forming an oxide electrical conductor after heat treatment such as calcination carried out in air or an oxidizing atmosphere, - Preferably, a nitrate of at least one metal element capable of forming an oxide electrical conductor after heat treatment such as calcination carried out in air or an oxidizing atmosphere, - Preferably an oxalate of at least one metallic element capable of forming an oxide electrical conductor after heat treatment such as calcination carried out in air or an oxidizing atmosphere, and - Preferably, an acetate of at least one metal element capable of forming an oxide electrical conductor after heat treatment such as calcination carried out in air or an oxidizing atmosphere, Selected from.

[0092] To obtain a layer of an electron conductor material on aggregates or aggregates of primary nanoparticles of at least one electrode active material P, preferably a layer of oxide electron conductor material from an alkoxide, nitrate, oxalate, or acetate, a colloidal suspension or paste containing aggregates or aggregates of nanoparticles can be brought into contact with a solution rich in a precursor of the desired electron conductor material.

[0093] This is a mixture of a colloidal suspension or paste containing aggregates or aggregates of primary nanoparticles of electrode active material P, and a precursor of at least one oxide electronic conductor material, which is then used to produce the porous dry layer and electrode according to the present invention. The mixture of the colloidal suspension or paste containing aggregates or aggregates of primary nanoparticles of electrode active material P and the precursor of at least one oxide electronic conductor material is hereinafter referred to as the "mixture according to the present invention." Advantageously, the mixture according to the present invention is in the form of a colloidal suspension or paste (ink).

[0094] 4. Fabrication of the porous layer The method for manufacturing an electrode according to the present invention includes the steps of applying a mixture containing a precursor of one or more oxide electronically conductive materials and a colloidal suspension or paste containing aggregates or aggregates of primary nanoparticles of at least one electrode active material P onto a substrate to form a layer, and then drying the layer to obtain a porous layer. This series of steps, including applying the mixture onto a substrate to form a layer and then drying, can be repeated multiple times to increase the thickness of the porous layer. The final thickness of the porous layer is advantageously 5 mm or less, preferably about 1 μm to about 500 μm. The thickness of the porous layer is advantageously less than 500 μm, preferably about 2 μm to about 400 μm, more preferably 2 μm to 300 μm, and even more preferably 3 μm to 200 μm. Generally, the mixture according to the present invention in the form of a colloidal suspension or paste is deposited onto a substrate by any suitable technique, specifically, electrophoresis, extrusion, additive manufacturing (or "robocasting"), inkjet printing, spray, flexographic printing, coating methods, preferably coating methods using a blade (known in terms of "doctor blade" or "tape casting"), roll coating, curtain coating, slot die extrusion, or dip coating.

[0095] In order to ensure that the mixture according to the present invention has a viscosity suitable for coating techniques commonly used in electrode manufacturing and can also be deposited on a substrate, it is advantageous to use the mixture according to the present invention in the form of a colloidal suspension or paste with a solid content of less than 30% by mass.

[0096] According to the applicant's findings, the applicant's knowledge indicates that when the average diameter of the nanoparticle aggregates or aggregates 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 the subsequent steps of the method.

[0097] According to the present invention, the porous layer can be deposited by inkjet printing or coating methods, particularly dip coating, roll coating, curtain coating, slot die coating, or doctor blade coating, which originate from a mixture according to the present invention in the form of a fairly concentrated suspension comprising a precursor of at least one oxide electronic conductor material and aggregates or aggregates of nanoparticles of the active material P.

[0098] The porous electrode layer can also be deposited by electrophoresis, in which case the mixture according to the present invention is advantageous to be used in the form of a low-concentration suspension containing aggregates of nanoparticles of at least one oxide electron conductor material precursor and the active material P.

[0099] The method for depositing the mixture according to the present invention by electrophoresis, extrusion, additive manufacturing, dip coating, inkjet, roll coating, curtain coating, doctor blade, or slot die coating is simple, safe, easy to implement and industrialize, and can yield a homogeneous final porous layer. Electrophoretic deposition allows for the uniform deposition of layers over a wide surface at a high deposition rate. In particular, the above-mentioned coating techniques simplify tank management compared to electrophoretic deposition techniques because the particles in the suspension are not depleted during deposition. Inkjet deposition allows for localized deposition.

[0100] A porous thick film layer, preferably having a thickness of 50 to 400 μm, can be manufactured in a single step by roll coating, curtain coating, slot die coating, doctor blade coating (i.e., using a blade), or extrusion.

[0101] The performance of the technique and method for depositing the mixture according to the present invention in the form of a colloidal suspension or paste (ink) must be compatible with the viscosity of the colloidal suspension or paste (ink) used, and vice versa.

[0102] The substrate is, advantageously, an intermediate substrate or a substrate that functions as a current collector.

[0103] 4.1 Circuit board capable of functioning as a current collector In the first embodiment, the substrate is capable of functioning as a current collector and is advantageously compatible with the heat treatment used in the method according to the present invention. The substrate may be a metal substrate, or in particular a substrate made of electronically conductive carbon based on graphite, graphene, and / or carbon nanotubes. The current collector function of the electrode is ensured by depositing the mixture according to the present invention on the substrate in the form of a colloidal suspension or paste (ink). The mixture according to the present invention in the form of a colloidal suspension or paste (ink) may be deposited on one or two surfaces of the substrate, particularly by the deposition technique described above.

[0104] The current collector in an electrochemical apparatus using the electrodes according to the present invention can be a stable substrate within the operating potential range of the electrochemical apparatus. Inside a battery using the electrodes according to the present invention, the current collector must be a stable substrate with respect to the lithium potential, preferably in a potential range of 2.5V to 5V for the positive electrode and 0V to 2.5V for the negative electrode. Advantageously, a metal substrate, such as a metal strip (i.e., a laminated metal sheet), is selected. The substrate can be made from tungsten, molybdenum, chromium, titanium, tantalum, zirconium, niobium, stainless steel, or alloys of two or more of these materials. Such metal substrates are expensive and can 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 and are therefore particularly suitable as sinterable electrode substrates. The reason for using these heat-resistant substrates is to allow for the sintering of preferably thin deposits directly deposited on the substrate.

[0105] Furthermore, the substrate, which can function as a current collector, may be coated with a conductive or semiconducting oxide before depositing the mixture according to the present invention in the form of a colloidal suspension or paste (ink). This allows for the protection of inexpensive substrates, particularly those made of copper, nickel, aluminum, or carbon, especially those in the form of graphite. Thus, these inexpensive substrates can be used as electrode substrates, particularly from a cost perspective. Conductive carbon sheets (typically graphite), metal sheets, or metallized nonmetal sheets (i.e., coated with a metal layer) can be used. 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 advantage of being stable over a wide potential range and resistant to heat treatment.

[0106] Copper, nickel, molybdenum, and their alloys are preferably used as negative electrode substrates. Carbon-based substrates, particularly graphite substrates, based on nickel-chromium alloys, stainless steel, chromium, titanium, aluminum, tungsten, molybdenum, tantalum, zirconium, niobium, or alloys containing at least one of these elements, are preferably used as current collector substrates for positive electrodes. These negative electrode substrates and / or positive electrode substrates may or may not be coated with an electrochemically inert conductive layer. Such layers can be produced by depositing nitrides, carbides, graphite, gold, palladium, and / or platinum.

[0107] The mixture according to the present invention can be applied in the form of a colloidal suspension or paste (ink) to one or both sides of a substrate that functions as a current collector. The layer deposited on this substrate is then dried to obtain a porous layer containing an electrode active material P and a precursor of at least one active electron conductor material.

[0108] Next, on this porous dry layer initially deposited on one or both sides of a substrate capable of functioning as a current collector, the conversion of one or more oxide electron conductor material precursors into oxide electron conductor materials is carried out.

[0109] 4.2 Intermediate board According to a second embodiment, the mixture according to the present invention is in the form of a colloidal suspension or paste comprising an electrode active material P and at least one active material electron conductor precursor (ink), and is deposited not on a substrate capable of functioning as a current collector, but typically on an intermediate substrate used temporarily.

[0110] In this embodiment, the mixture according to the present invention, in the form of a colloidal suspension or paste (ink), is deposited on the surface of an intermediate substrate, and the resulting layer can then be easily separated from the intermediate substrate.

[0111] In particular, a mixture according to the present invention in the form of a suspension or paste containing a precursor of at least one oxide electronic conductor material and aggregates and / or clumps of nanoparticles of electrode active material P, preferably a concentrated suspension (i.e., low fluidity and preferably paste-like) containing a precursor of at least one oxide electronic conductor material and aggregates and / or clumps of nanoparticles of electrode active material P, can be used to deposit a relatively thick layer called a "green sheet". These thick layers can be deposited by any suitable means, particularly inkjet printing, extrusion, additive manufacturing, spray printing, flexographic printing, coating, preferably doctor blade coating, roll coating, curtain coating, slot die extrusion, or dipping.

[0112] Methods for depositing nanoparticles by dip coating, inkjet printing, roll coating, curtain coating, slot die coating, extrusion, additive manufacturing, spray, flexographic printing, or doctor blade coating are simple, safe, easy to implement and industrialize, and can yield homogeneous deposits. Inkjet printing, as with doctor blade under a mask, allows for localized deposition of the mixture according to the present invention. Roll, curtain, slot die, dipping, extrusion, additive manufacturing, or doctor blade coating techniques allow for obtaining thick layers in a single step.

[0113] The intermediate substrate can be a flexible substrate, for example, a polymer sheet such as polyethylene terephthalate (abbreviated as PET). In this second embodiment, the deposition process is preferably performed on one side of the intermediate substrate in order to facilitate separation of the layer from the substrate. In this second embodiment, the layer is separated from the substrate after drying and before high-temperature heat treatment. The thickness of the layer after drying is preferably 5 mm or less, preferably about 1 μm to about 600 μm. The thickness of the layer after drying is preferably less than 500 μm, preferably about 3 μm to about 400 μm, more preferably 3 μm to 300 μm.

[0114] In the second embodiment described above, a method for manufacturing electrodes for an electrochemical device such as a battery preferably uses an intermediate substrate made of a polymer (e.g., PET) to obtain a strip called a "green strip". After drying, the green strip is peeled off the substrate to form a self-standing plate or sheet (hereinafter, the term "plate" will be used regardless of its thickness).

[0115] Next, on these self-supporting porous plates or sheets, the conversion of one or more oxide electron conductor material precursors into oxide electron conductor materials is performed.

[0116] 5. Conversion of one or more oxide electronic conductor material precursors present in the porous dry layer to oxide electronic conductor materials. A self-supporting porous dry layer or porous plate containing an electrode active material P and a precursor of at least one active material electron conductor is heat-treated, preferably in air or an oxidizing atmosphere, at a temperature sufficient to convert the precursor of the one or more oxide electron conductors into oxide electron conductors. Thus, regions of the electrode active material P are formed that are at least partially covered by a coating of an electron conductor material, preferably an oxide electron conductor material, more preferably aluminum-doped SnO2, aluminum-doped ZnO (ZnO:Al, preferably with a molar ratio of Zn:Al of 1:0.015 to 1:0.05), In2O3, Ga2O3, MoO3, or SrMoO3, wherein the coating completely disperses a mixture of two of these oxides, for example, a coating containing 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, throughout the entire internal volume of the electrode and on the surface.

[0117] This heat treatment is preferably carried out in an oxidizing atmosphere and can remove organic components, i.e., debinding. Depending on the properties of the electrode active material P used and the temperature used to convert the precursor of one or more oxide electronic conductor materials into oxide electronic conductor materials, this heat treatment can also solidify the layer or porous plate, which will be described in detail in the next section.

[0118] With regard to the prior art, in relation to porous electrodes with carbon coatings on and inside the pores of the electrode, as described in International Publication No. 2021 / 220174, the presence of regions of the electrode active material P that are at least partially covered with a coating of an oxide electron conductor material, preferably regions covered with the oxide electron conductor material coating, which are completely dispersed throughout the entire internal volume of the electrode and on the surface, improves the electrochemical performance of the electrode at high temperatures and significantly improves the stability of the electrode. More specifically, by using this unique three-dimensional structure which includes regions of the electrode active material P that are at least partially covered with a coating of an oxide electron conductor material, preferably electrode active material P that are covered with the oxide electron conductor material coating throughout the entire internal volume of the electrode and on the surface, the performance of the final electrode is particularly improved. More specifically, the presence of at least partially covered regions of electrode active material P, preferably regions covered with a coating of oxide electronic conductor material, which are completely dispersed throughout the entire internal volume of the electrode and on the surface, improves the final properties of the electrode, particularly improving the voltage stability and temperature stability of the electrode, improving the electrochemical stability of the electrode, and reducing the resistance to polarization of the electrode, especially when in contact with a liquid electrolyte, and similar effects can be obtained even when the electrode is thick. When the electrode is thick, and / or when the resistance of the active material in the porous layer is too high, it is particularly advantageous to use an electronic conductor in the form of an oxide, particularly In2O3, SnO2, aluminum-doped ZnO (ZnO:Al, preferably with a molar ratio of Zn:Al of 1:0.015 to 1:0.05), Ga2O3, MoO3, SrMoO3, or a mixture of one or more of these oxides or doped oxides, in the volume of the electrode.

[0119] The electrode according to the present invention is porous, preferably mesoporous, and preferably has a large specific surface area. Increasing the specific surface area of ​​the electrode increases the exchangeable surface area and thereby improves the power of the battery, but at the same time accelerates parasitic reactions. The presence of these electron-conducting coatings in the form of oxides within the electrode volume can inhibit these parasitic reactions.

[0120] Furthermore, due to their extremely large specific surface area, these oxide-form electron-conducting coatings have a significantly greater effect on the electron conductivity of electrodes than conventional electrodes with smaller specific surface areas, and this is true even when the thickness of the deposited conductive coating is thin. These oxide electron-conducting coatings placed within the electrode volume of a porous layer impart excellent electron conductivity to the electrode, especially when the porous layer is formed from an electrode active material with low electron conductivity. This layer of oxide electron-conducting material can improve the electron conductivity of the electrode while suppressing electrode dissolution, thereby improving the power of the battery. This is all the more pronounced because the thickness of the coating layer of oxide electron-conducting material having regions of electrode active material P is thin.

[0121] This is essentially a unique structure of a porous electrode manufactured according to the method of the present invention, comprising regions of electrode-active material P covered with a coating of oxide electron-conducting material throughout the entire internal volume of the electrode and on the electrode surface, thereby improving the final properties of the electrode and making it possible to obtain a thick electrode without increasing the internal resistance of the electrode.

[0122] The thickness of the oxide electronically conductive material coating covering the electrode active material P throughout the entire internal volume of the electrode is typically 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 coating of oxide electronically conductive material throughout the entire internal volume of the electrode advantageously has an optimal thickness. This coating must be thick enough to improve electronic conductivity, thin enough not to hinder ion conduction within the electrode, and ultimately thin enough not to degrade the performance of electrical energy storage or generation devices such as batteries. Furthermore, this coating provides good electronic conductivity to the electrode due to the large specific surface area of ​​the electrode.

[0123] Advantageously, the oxide electronic conductor material may include an oxide electronic conductor material, preferably the oxide electronic conductor material is -Tin oxide (SnO2), aluminum-doped zinc oxide (ZnO:Al), preferably with a Zn:Al molar ratio of 1:0.015 to 1:0.05, indium oxide (In2O3), gallium oxide (Ga2O3), molybdenum oxide (MoO3), strontium molybdenum oxide (SrMoO3), mixtures of two of these oxides, for example, indium tin oxide corresponding to a mixture of indium oxide (In2O3) and tin oxide (SnO3), 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), - A molybdenum oxide-based doped oxide, preferably 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 doped with 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), Selected from.

[0124] 6. Solidification of a porous layer containing an electrode active material P and an oxide electron conductor material to obtain a porous, preferably mesoporous, electrode. Next, the porous layer or self-supporting porous plate can be heat-treated, preferably in an oxidizing atmosphere, if necessary, to remove organic components. Next, the porous layer or self-supporting porous plate can be solidified. This solidification can be carried out by pressurization and / or heat treatment, i.e., heat treatment (heating), heat treatment preceding mechanical treatment, and optionally thermomechanical treatment, typically hot compression. In a very advantageous embodiment of the present invention, by this treatment, on the one hand, the primary nanoparticles are partially aggregated into aggregates or agglomerates, and on the other hand, due to the presence of the coating of the oxide electron-conducting material, the adjacent aggregates or agglomerates are partially aggregated. This phenomenon is called "necking" or "neck formation". This is characterized in that two contacting particles are partially aggregated and they remain separated but are connected by a (restricted) neck. Lithium ions and electrons can move within these necks and diffuse from particle to particle without encountering grain boundaries. The nanoparticles are welded to each other so that electrons can conduct between them. Adjacent aggregates or agglomerates are welded to each other via a coating of the oxide electron conductor, enabling electrons to conduct from one aggregate or agglomerate to another. Electron conduction occurs by two different means, specifically, the nanoparticles of the electrode active material P (1) welded to each other and the adjacent aggregates or agglomerates welded to each other via the oxide electron-conducting material (2). This is schematically shown in FIG. 1.

[0125] In this way, a rigid mesoporous film is formed from the primary nanoparticles of the electrode active material P (1) and the oxide electron-conducting material (2) without using an organic binder, forming a three-dimensional network having high ion mobility and electron conductivity. This network includes interconnected pores, preferably mesoporous pores. The porous layer thus obtained, preferably a mesoporous layer, is very suitable for impregnating the pores of the electrode with an ion-conducting material, and the ion-conducting material penetrates deep into the open porous structure of the layer.

[0126] The temperature required to obtain "necking" varies depending on the material, and considering the diffusivity of the phenomenon causing necking, the processing time is temperature-dependent. This method is also called sintering, and depending on the processing time and temperature, significant fusion (necking) occurs, albeit with some degree of difference, which affects the porosity. Thus, an electrode with a desired porous or mesoporous ceramic structure with a controlled porosity can be obtained while maintaining a completely homogeneous channel size. Through this thermomechanical treatment or heat treatment, the electrode layer is removed from organic components and residues (such as the liquid phase of a suspension containing nanoparticles, binders, and optionally surfactants), becoming an inorganic (ceramic) layer.

[0127] The thickness of the porous electrode or porous plate thus disposed at the center is preferably 5 mm or less, and preferably about 1 μm to about 500 μm. The thickness of the porous plate after sintering is preferably 2 μm to 400 μm, more preferably 2 μm to 300 μm, and even more preferably 3 μm to 200 μm.

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

[0129] When the conductive sheet is a metal, it is preferably a laminated sheet, i.e., a sheet obtained by lamination. After lamination, final annealing can be performed as necessary. According to metallurgical terms, the final annealing can be (entire or partial) softening annealing or recrystallization. Also, a sheet obtained by electrolytic deposition, such as an electrodeposited copper sheet or an electrodeposited nickel sheet, can be used.

[0130] After solidification (i.e., sintering), this conductive sheet is placed on a plate or inserted between two pre-fabricated plates. Subsequently, by press-forming this assembly, the thin layer of intermediate conductive adhesive promotes adhesion between the plate and the substrate, forming a plate / substrate or plate / substrate / plate assembly, resulting in a rigid, integrated subassembly.

[0131] One of the advantages of the second embodiment is that it allows the use of inexpensive substrates such as aluminum strips, copper strips, and graphite strips. More specifically, although these strips cannot withstand the heat treatment required to solidify the deposited layer, their oxidation can be prevented by bonding them to the plate after the heat treatment.

[0132] The resulting plate / substrate or plate / substrate / plate subassembly can be used in the manufacture of electrochemical devices such as batteries.

[0133] Optionally, the electrode according to the present invention, preferably a self-supporting porous plate, can be impregnated with an ion-conducting phase, i.e., a phase comprising at least one ion-conducting material, such as an ion-conducting polymer or an ion liquid polymer. This ion-conducting material may also be electronically conductive. The ion-conducting material can be of different types. These may be liquid, gel-like, or solid. Impregnation with a solid ion conductor is advantageously carried out by using a molten ion conductor or an ion conductor dissolved in a solvent that is subsequently evaporated. The ion-conducting phase may contain 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] By impregnating the pores of a porous electrode, preferably the pores of a self-supporting porous plate, with an ion-conducting polymer, the mechanical rigidity of the porous electrode is improved. By using a porous electrode impregnated with the ion-conducting polymer according to the present invention in an energy storage device or energy generation device such as a battery, its lifespan can be extended.

[0135] Optionally, an electrically insulating layer with good ionic conductivity can be deposited on the porous electrode according to the present invention, the thickness of which is typically about 0.5 nm to 20 nm, preferably less than 5 nm, and more preferably less than 2 nm.

[0136] The ion-conductive and electrically insulating layer can be inorganic or organic. More specifically, usable inorganic layers include, for example, lithium ion oxides, phosphates, or borate conductors, and usable organic layers include polymers (e.g., PEO optionally containing lithium salts, or tetrafluoroethylene sulfonate copolymers such as Nafion® (CAS number 31175-20-9)). This ion-conductive and electrically insulating layer must be stable in contact with the electrode on which it is deposited. It is preferable to use a lithium ion-conductive borate for the positive electrode.

[0137] In electrodes made of LiMn2O4, there is a risk of manganese dissolving in certain liquid electrolytes, especially at high temperatures. Therefore, an ion-conductive and electrically insulating layer can limit the dissolution of ions from the electrode and the movement of ions into the electrolyte.

[0138] When the electrode according to the present invention is covered with an ion-conducting layer, the ion-conducting layer primarily ensures the above-mentioned protective function (particularly the prevention of electrode dissolution).

[0139] In summary, the presence of regions of electrode active material P covered, preferably with a coating of an oxide electronically conductive material, throughout the entire internal volume and on the surface of the porous electrode according to the present invention, allows for at least improved electronic conductivity and, depending on the properties of the oxide electronically conductive material, can advantageously provide protection against the dissolution of the electrode into the electrolyte at high temperatures. If these two effects are obtained by a single arrangement of oxide electronically conductive material throughout the entire internal volume and on the surface of the electrode according to the present invention, or if this particular arrangement of oxide electronically conductive material throughout the entire internal volume of the electrode according to the present invention is insufficient to obtain the two effects, it is possible to deposit, for example, an ionic conductive and electrically insulating layer on and inside the pores of the electrode according to the present invention to obtain further protection at high temperatures.

[0140] According to the first and second embodiments, a porous electrode according to the present invention is obtained, which is placed on a metal substrate that functions as a current collector, or located on both sides of a metal substrate that functions as a current collector. The electrode / substrate / electrode subassembly thus obtained according to the first or second embodiment can be used in the manufacture of electrochemical devices such as batteries, in particular microbatteries. Assembly by thermal welding can also be performed by stacking and thermal pressing assemblies of the structure of an electrochemical device (battery, in particular microbattery, etc.), in which case a multilayer laminate is assembled including a first negative electrode according to the present invention, its metal substrate, a second negative electrode according to the present invention, a solid electrolyte layer or electrolytic separator, a first positive electrode according to the present invention, its metal substrate, a second positive electrode according to the present invention, a new solid electrolyte layer or new electrolytic separator, and so on.

[0141] This electrode / substrate / electrode subassembly can be used to manufacture electrochemical devices such as batteries (especially microbatteries). Regardless of the embodiment of the electrode / substrate / electrode subassembly, an electrolyte film or electrolyte separator is deposited on top of the latter. Next, the necessary cutting is performed to manufacture a battery with multiple basic cells, the subassemblies are stacked (usually "head to tail"), and thermocompression bonding is performed to weld them together with the negative and positive electrodes of the solid electrolyte.

[0142] Alternatively, the cutting required to manufacture a battery having multiple basic cells can be performed before depositing the electrolyte film or electrolytic separator onto each negative electrode / substrate / negative and positive electrode / substrate / positive subassembly. Next, the negative electrode / substrate / negative subassembly and / or positive electrode / substrate / positive subassembly are covered with the electrolyte film or electrolytic separator, then the subassemblies are laminated, and the negative electrode and positive electrode are welded to the electrolyte film or electrolytic separator by thermocompression bonding, and if necessary, the resulting laminate is impregnated with a phase supporting the electrolyte, preferably lithium ions, sodium ions, or potassium ions.

[0143] In the two alternative examples presented, particularly when the electrodes according to the present invention are impregnated with an ion-conducting material such as an ion-conducting polymer or ion liquid polymer, welding by thermocompression can be performed at a relatively low temperature. For this reason, oxidation of the metal layer of the substrate is not observed. [Examples]

[0144] Example 1: Production of a LiMn2O4-based mesoporous cathode according to the present invention LiMn2O4 nanoparticle aqueous suspension, Liddle et al.'s paper "Li 1+x Mn 2-y The compound was prepared by hydrothermal synthesis according to the method described in "Novel One-Pot Hydrothermal Synthesis and Electrochemical Characterization of O4 Spinel Structure Compounds" (Energy & Environmental Science (2010) vol.3, 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 this liquid phase was poured into an autoclave. While stirring, 28 ml of isobutyraldehyde and water were added to a total volume of 3.54 L. Next, the autoclave was heated to 180°C and maintained at this temperature for 6 hours. After slow cooling, a black precipitate suspended in the solvent was obtained. This precipitate was subjected to a series of centrifugation steps (redispersion in water) to obtain an aggregated suspension with a conductivity of approximately 300 μS / cm and a zeta potential of -30 mV. The obtained aggregates were formed from aggregated primary particles with a size of 10-20 nm. The obtained aggregates were spherical with an average diameter of approximately 150 nm and were characterized by X-ray diffraction and electron microscopy. A series of centrifugation steps (redispersion in water) were performed on this precipitate to obtain an aggregated suspension with an electrical conductivity of approximately 300 μS / cm and a zeta potential of -30 mV. The obtained aggregates were formed from aggregated primary particles with a size of 10-20 nm. The obtained aggregates were spherical with an average diameter of approximately 150 nm and were characterized by X-ray diffraction and electron microscopy.

[0145] 1 g of polyvinylpyrrolidone (abbreviated as PVP) with a molar mass of 55,000 g / mol was added to 50 mL of distilled water at 40 °C, and then 3 g of tin acetate was added to this PVP aqueous solution.

[0146] The LiMn2O4 suspension was reconcentrated by centrifugation, and the pellets were redispersed in a required amount of water to obtain a 16 wt% paste. Next, an aqueous solution containing PVP and tin acetate in an amount such that the ratio of tin acetate to LiMn2O4 was 10 mass% and a required amount of water were added to the LiMn2O4 suspension of nanoparticle aggregates to obtain an aggregate suspension with a solid content of 10%.

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

[0148] Next, this layer was heat-treated at 600 °C in air for 5 hours. On the one hand, tin acetate, which is a precursor of the oxide electron conductor material, was converted to SnO2, that is, the oxide electron conductor material, to remove reaction by-products. On the other hand, the primary nanoparticles were welded due to the presence of the formed oxide electron conductor material SnO2, and adjacent aggregates were also welded to improve the adhesion to the substrate and complete the recrystallization of LiMn2O The porous layer thus obtained has an open porosity of about 45% by volume, and the pore size is 10 nm to 20 nm.

[0149] Example 2: Preparation of Li4Ti5O 12 Production of mesoporous negative electrode of the system Li4Ti5O 12A suspension of nanoparticles was prepared. 190 mL of 1,4-butanediol was poured into a beaker, and 4.25 g of lithium acetate was added while stirring. The solution was left undisturbed until the acetate was completely dissolved. Next, 16.9 g of titanium butoxide was placed under an inert atmosphere and added to the acetate solution. After stirring the solution for several minutes, it was transferred to an autoclave containing 60 mL of butanediol that had been added beforehand. The autoclave was then closed and purged with nitrogen for at least 10 minutes. The autoclave was then heated to 300°C at a rate of 3°C / min and maintained at this temperature for 2 hours while stirring. Finally, it was cooled while continuously stirring.

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

[0151] One 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 three g of tin acetate was added to this PVP solution.

[0152] Li4Ti5O 12 Li4Ti5O 12 A solution of PVP and tin acetate was added in an amount such that the mass ratio of tin acetate to PVP was 10% by mass. Ethanol was evaporated until the solid content of the aggregate suspension was 10%. The ink thus obtained was applied to a 5 μm thick stainless steel (316L) strip. The resulting layer was dried in a temperature and humidity controlled oven to prevent cracking during drying. Next, the deposition and drying of the ink was repeated to obtain a layer approximately 4 μm thick. Next, this layer was heat-treated in air at 600°C for 5 hours. This heat treatment converted tin acetate, a precursor of the oxide electronic conductor material, to SnO2, i.e., the oxide electronic conductor material, removed reaction byproducts, and covered with a uniform SnO2 coating of Li4Ti5O 12A porous layer containing aggregates of nanoparticles is formed, the layer is solidified, i.e., the primary particles of the nanoparticles are welded together, and the formed oxide electron conductor material SnO2 is welded to adjacent aggregates, resulting in Li4Ti5O covered with a SnO2 coating. 12 To improve the adhesion of nanoparticle aggregates to the substrate, Li4Ti5O 12 The recrystallization process can be completed.

[0153] Example 3: Manufacturing of a battery using a porous positive electrode and a porous negative electrode 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 56 ml of water was added while vigorously stirring the medium to obtain solution A. 4.0584 g of H3PO4 was diluted in 105.6 ml of water, and 45.6 ml of ethanol was added to this solution to obtain the second solution (hereinafter referred to as solution B).

[0154] Next, solution B was added to solution A while vigorously stirring. The resulting solution became completely clear after the bubbles that had formed during mixing disappeared. This solution was added to 1.2 liters of acetone using an Ultraturrax® homogenizer, and the medium was homogenized. Immediately afterward, a white precipitate was observed suspended in the liquid phase.

[0155] The reaction medium was homogenized for 5 minutes, then held under magnetic stirring for 10 minutes. It was then decanted for 1-2 hours. The supernatant was discarded, and the remaining suspension was centrifuged at 6000 rpm for 10 minutes. Next, 300 ml of water was added to return the precipitate to the suspension (using sonotrode and magnetic stirring). With vigorous stirring, 125 ml of 100 g / l sodium tripolyphosphate solution was added to the resulting colloidal suspension. The suspension became more stable. Next, the suspension was sonicated using sonotrode. Next, the suspension was centrifuged at 8000 rpm for 15 minutes. Next, the pellet was redispersed in 150 ml of water. Next, the resulting suspension was centrifuged again at 8000 rpm for 15 minutes, and the resulting pellet was redispersed in 12 ml of water.

[0156] Aggregates of approximately 100 nm in size, formed from primary particles of Li3PO4, were obtained in a suspension in water.

[0157] Fabrication of porous inorganic layers on pre-formed negative and positive electrode layers from the Li3PO4 nanoparticle suspension described above in ba) A thin, porous Li3PO4 layer with a thickness of approximately 3 μm was deposited by coating the surfaces of pre-fabricated negative and positive electrodes with a pre-prepared suspension of Li3PO4 nanoparticles. To remove trace amounts of organic residue, this layer was dried in air at 120°C and then calcined in air at 350°C for 1 hour.

[0158] c. Manufacturing of electrochemical cells After depositing a 3 μm porous Li3PO4 film onto each of the pre-fabricated electrodes (Examples 1 and 2), the two subsystems were stacked so that the Li3PO4 thin films were in contact with each other. This stack was then hot-pressed under vacuum.

[0159] To carry this out, the laminate is placed under a pressure of 1.5 MPa, and then 10 -3 The material was vacuum-dried in a bar for 30 minutes. Then, the press plate was heated to 450°C at a rate of 4°C / second. At 450°C, the laminate was thermally compressed under a pressure of 45 MPa for 1 minute, after which the system was cooled to room temperature.

[0160] Upon completion of the assembly, a rigid, multilayer system formed from one or more assembled battery cells was obtained.

[0161] Next, this assembly was immersed in an electrolyte solution containing 0.7M LiTFSI dissolved in PYR14TFSI. The electrolyte instantly penetrated into the pores by capillary action. After immersing the system for 1 minute, the surface of the cell stack was dried with an N2 blade.

Claims

1. A method for manufacturing a porous electrode, particularly a porous electrode for an electrical energy storage or generation device, wherein the electrode is a porous layer comprising at least one electrode active material P and an oxide conductive material, the electrode is binder-free, has a porosity of 25% to 60% by volume, preferably 25% to 50% by volume, and has pores with an average diameter of less than 100 nm, and the manufacturing method comprises the following steps: (a) A step of providing a colloidal suspension or paste comprising an aggregate or aggregate consisting of a substrate, a precursor of at least one oxide conductive material, and primary nanoparticles of at least one electrode active material P, wherein the primary mean diameter D of the primary nanoparticles ５０ The midrange is 2 nm to 400 nm, preferably 2 nm to 100 nm, more preferably 2 nm to 60 nm, and the aggregate or aggregate mass has a median diameter D of 50 nm to 900 nm, preferably 100 nm to 800 nm. ５０ The process is understood to include the fact that the substrate can be a substrate or intermediate substrate capable of functioning as a current collector. (b) A step of mixing one or more oxide conductive material precursors with the colloidal suspension or paste containing aggregates or aggregates of primary nanoparticles of at least one electrode active material P provided in step (a) to form a mixture, (c) A step of forming a layer 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, and coating, preferably doctor blade coating, roll coating, curtain coating, dip coating, or slot die coating. (d) A step of drying the layer obtained in step (c) to obtain a dried layer, wherein, if necessary, after drying step (d), a step of separating the dried layer from the intermediate substrate. (e) A step of converting one or more precursors of oxide conductive materials into oxide conductive materials in order to include the oxide conductive material in the dry layer, (f) A step of solidifying the layer 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 during the same heat treatment. A method for manufacturing porous electrodes, including

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

3. After step (f), an electrolyte, preferably, is placed in the pores of the porous electrode. - An electrolyte comprising at least one aprotic solvent and at least one lithium salt, sodium salt, or potassium salt; - An electrolyte comprising 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 salt, sodium salt, or potassium salt; - Ionic liquid polymer; - A polymer made ionically conductive by the addition of at least one of the following: lithium salt, sodium salt, or potassium salt; - A polymer made into an ion conductor by adding a liquid electrolyte to either the polymer phase or the porous structure of the porous electrode, or by an ion-conducting polymer, preferably an ion-conducting polymer 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); A method for producing a porous electrode according to claim 1 or 2, characterized by impregnating the electrode with a phase supporting lithium ions, sodium ions, or potassium ions selected from the group consisting of the following:

4. The precursor of one or more oxide electronic conductor materials, after heat treatment such as calcination, Selected from organic salts containing one or more metal elements capable of forming an electrical conductor, the conversion to the electrical conductor material is preferably carried out by a heat treatment such as calcination in air or an oxidizing atmosphere, and these organic salts are preferably the following - Preferably an alkoxide of at least one metallic element capable of forming an oxide electrical conductor after heat treatment such as calcination carried out in air or an oxidizing atmosphere, - Nitrate of at least one metal element capable of forming an oxide electrical conductor after heat treatment such as calcination carried out in air or an oxidizing atmosphere, - Preferably, an oxalate of at least one metal element capable of forming an oxide electrical conductor after heat treatment such as calcination carried out in air or an oxidizing atmosphere, - Preferably, an acetate of at least one metal element capable of forming an oxide electrical conductor after heat treatment such as calcination carried out in air or an oxidizing atmosphere, - and / or, preferably, the metal element is tin, zinc, indium, gallium, molybdenum, or a mixture of two, three, four, or five of these elements. A method for manufacturing a porous electrode according to any one of claims 1 to 3, characterized by being selected from among.

5. The aforementioned oxide electronic conductor material is - Tin oxide (SnO ２ ), zinc oxide doped with aluminum (ZnO:Al), preferably with a molar ratio of Zn:Al of 1:0.015 to 1:0.05, indium oxide (In ２ O ３ ), gallium oxide (Ga ２ O ３ ), molybdenum oxide (MoO ３ ), strontium molybdate (SrMoO ３ ), a mixture of two of these oxides, for example indium tin oxide corresponding to a mixture of indium oxide (In ２ O ３ ) and tin oxide (SnO ３ ), 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, - A zinc oxide-based doped oxide, preferably one 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), - A molybdenum oxide-based doped oxide, preferably 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 doped with 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), A method for manufacturing a porous electrode according to any one of claims 1 to 4, characterized by being selected from among.

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

7. The porous electrode obtained at the end of step (f) is 10m ２ / g to 500m ２ Having a specific surface area of ​​ / g, and / or If the substrate is a substrate capable of functioning as a current collector, it has a thickness of 2 μm to 20 μm, and / or The method for manufacturing a porous electrode according to any one of claims 1 to 5, characterized in that, when the substrate is an intermediate substrate, it has a thickness of 25 μm to 500 μm, and more preferably has a thickness of 50 μm to 400 μm.

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

9. A 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) comprises 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, and it is understood that this heat treatment and steps (e) and / or (f) can be carried out in the same heat treatment step.

10. The electrode active material P is - LiMn oxide ２ O ４ Li １＋ｘ Mn ２－ｘ O ４ (0 < x < 0.15), LiCoO ２ LiNiO ２ LiMn １．５ Ni ０．５ O ４ LiMn １．５ Ni ０．５－ｘ X ｘ O ４ (Here, X is selected from Al, Fe, Cr, Co, Rh, Nd, and other rare earth elements (e.g., Sc, Y, Lu, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), where 0 < x < 0.1.) LiMn ２－ｘ M ｘ O ４ (M = Er, Dy, Gd, Tb, Yb, Al, Y, Ni, Co, Ti, Sn, As, Mg, or a mixture thereof, where 0 < x < 0.4.) LiFeO ２ LiMn １／３ Ni １／３ Co １／３ O ２ LiNi ０．８ Co ０．１５ Al ０．０５ O ２ LiAl ｘ Mn ２－ｘ O ４ (Here, 0 < x < 0.15.) LiNi １／ｘ Co １／ｙ Mn １／ｚ O ２ (x + y + z = 10); -Li ｘ M ｙ O ２ (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 O ２ ; -Li １＋ｘ Nb ｙ Me ｚ A ｐ O ２ (Here, Me is at least one transition metal selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, where 0.6 < x < 1, 0 < y < 0.5, 0.25 ≤ z < 1, A ≠ Me and A ≠ Nb, and 0 ≤ p ≤ 0.20.) -Li ｘ Nb ｙ－ａ N ａ M ｚ－ｂ P ｂ O ２－ｃ F ｃ (Here, 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 M, N, and P are one or more elements 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, respectively.) -L) １．２５ Nb ０．２５ Mn ０．５０ O ２ ;L) １．３ Nb ０．３ Mn ０．４０ O ２ ;L) １．３ Nb ０．３ Fe ０．４０ O ２ ;L) １．３ Nb ０．４３ Ni ０．２７ O ２ ;L) １．３ Nb ０．４３ Co ０．２７ O ２ ;L) １．４ Nb ０．２ Mn ０．５３ O ２ ; -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 O ２ ; -LiNi ｘ Co ｙ Mn １－ｘ－ｙ O ２ (where 0 ≤ x and y ≤ 0.5); LiNi ｘ Ce ｚ Co ｙ Mn １－ｘ－ｙ O ２ (where 0 ≤ x, y ≤ 0.5, and 0 ≤ z); - LiFePO phosphate ４ LiMnPO ４ LiCoPO ４ LiNiPO ４ Li ３ V ２ (PO ４ ) ３、 Li ２ MPO ４ F (M = Fe, Co, Ni or a mixture of these different elements), LiMPO ４ F (M = V, Fe, T or a mixture of these different elements); formula LiMM'PO ４ Phosphates of (where M and M' (M≠M') are selected from Fe, Mn, Ni, Co, V, for example LiFe) ｘ Co １－ｘ PO ４ (Here, 0 < x < 1); -Fe ０．９ Co ０．１ OF;FeF ３ ;L-MSO ４ F(M=Fe、Co、Ni、M.、Z.、Mg); - Titanium oxysulfide (TiO ｙ S ｚ , z = 2 - y and 0.3 ≤ y ≤ 1), tungsten oxysulfide (WO ｙ S ｚ , 0.6 < y < 3 and 0.1 < z < 2), CuS, CuS ２ Li ｘ V ２ O ５ (0 < x ≤ 2), Li ｘ V ３ O ８ (0 < x ≤ 1.7), Li ｘ TiS ２ (0 < x ≤ 1), lithium titanium oxysulfide (Li ｘ TiO ｙ S ｚ (z = 2 - y, 0.3 ≤ y ≤ 1 and 0 < x ≤ 1), Li ｘ WO ｙ S ｚ (z = 2 - y, 0.3 ≤ y ≤ 1 and 0 < x ≤ 1), Li ｘ CuS (0<x≦1), Li ｘ CuS ２ (0 < x ≤ 1); Selected from group (A) consisting of, -Transition metal oxides: Na ｘ MO ２＋ｚ (where M is selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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 (u + v = 2, and M and M' are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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, 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 O ２ (0.67 ≤ x ≤ 1.0; 0.5 ≤ y ≤ 0.7 and 0.1 ≤ z ≤ 0.3); - Prussian blue and / or Prussian blue analogs, known by the abbreviation PBA: Na is a transition metal or a transition metal alloy. ｘ M １ [M ２ (CN) ６ ] ｙ . nH ２ O(M) １ M is a transition metal or a transition metal alloy. ２ ' is a transition metal, and 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); - Polyanionic compounds: Na ｘ M ２ (XO ４ ) ３ (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W), e.g., Na ３ V ２ (PO ４ ) ３ ; Na ｘ M ３ (XO ４ ) ２ (X ２ O ７ ) (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); Na ｘ M(X) ２ O ７ ) (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); Na ｘ M ２ (XO ４ ) ２ F ３ (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); Na ｘ M ２ (XO ４ ) ２ F ３－ｙ O ｙ (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, 0.07 ≤ y ≤ 0.12 and X = P, S, As, Si, Mo or W); Na ｘ M ２ O ２ (XO ４ ) ２ F (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); Na ｘ MXO ４ (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, X = P, S, As, Si, Mo or W); Among the group (B) consisting of, -Transition metal oxides: ・K ｘ MO ２＋ｚ (M is selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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 (u + v = 2 and M, M' is selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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 (u + v + w = ​​3 and M, M', M'' are selected from Mg, Ca, Li, Mn, Ni, Co, Cr, Sc, Te, 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 O ２ (0.67 ≤ x ≤ 1.0; 0.5 ≤ y ≤ 0.7 and 0.1 ≤ z ≤ 0.3); - Prussian blue and / or Prussian blue analogs, known by the abbreviation PBA: ・K ｘ M １ [M ２ (CN) ６ ] ｙ . nH ２ O(M) １ M is a transition metal or a transition metal alloy. ２’ x is a transition metal or a transition metal alloy, and the transition metal and the transition metal alloy are selected from Fe, Ni, Co, and Mn (0 ≤ x ≤ 2; y ≤ 1 and 0 ≤ n ≤ 12); - Polyanionic compounds: ・K ｘ M ２ (XO ４ ) ３ (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, and X = P, S, As, Si, Mo or W) For example, Na ３ V ２ (PO ４ ) ３ ; ・K ｘ M ３ (XO ４ ) ２ (X ２ O ７ ) (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, and X = P, S, As, Si, Mo or W); ・K ｘ M(X) ２ O ７ ) (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, and X = P, S, As, Si, Mo or W); ・K ｘ M ２ (XO ４ ) ２ F ３ (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, and X = P, S, As, Si, Mo or W); ・K ｘ M ２ (XO ４ ) ２ F ３－ｙ O ｙ (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, 0.07 ≤ y ≤ 0.12, and X = P, S, As, Si, Mo or W); ・K ｘ M ２ O ２ (XO ４ ) ２ F (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, and X = P, S, As, Si, Mo or W); ・K ｘ MXO ４ (0 < x ≤ 4, M = V, Fe, Cr, Mn, Co, Ni or Sc, and X = P, S, As, Si, Mo or W), A method for producing a porous electrode according to any one of claims 1 to 9, characterized in that it belongs to the group (C) consisting of the above.

11. The electrode active material P is -Li ４ Ti ５ O １２ 、Li ４ Ti ５－ｘ M ｘ O １２ (M = V, Zr, Hf, Nb, Ta, and 0 ≤ x ≤ 0.25); - Niobium oxide, and mixed oxides of niobium with titanium, germanium, cerium, or tungsten, preferably, ・N ２ O ５±δ 、Nb １２ WO ３３±δ 、Nb １４ W ３ O ４４±δ 、Nb １８ W １６ O ９３±δ 、Nb １６ W ５ O ５５±δ (0≦δ≦2)L-NLO ３ 、 ・TiNb ２ O ７±δ Li ｗ TiNb ２ O ７ (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 [Here, M １ and M ２ Each of these is at least one 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 These can be the same or different from each other, and 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2, and 0 ≤ δ ≤ 0.

3. La ｘ Ti １－２ｘ Nb ２＋ｘ O ７ [Here, 0 < x < 0.5.] ・M ｘ Ti １－２ｘ Nb ２＋ｘ O ７±δ [Here, M is an element with an oxidation value of +III, more specifically, M is at least one element selected from the group consisting of Fe, Ga, Mo, Al, and B, where 0 < x ≤ 0.20 and -0.3 ≤ δ ≤ 0.3.]; Ga ０．１０ Ti ０．８０ Nb ２．１０ O ７ Fe ０．１０ Ti ０．８０ Nb ２．１０ O ７ ; ・M ｘ Ti ２－２ｘ Nb １０＋ｘ O ２９±δ [Here, M is an element with an oxidation value of +III, more specifically, M is at least one element selected from the group consisting of Fe, Ga, Mo, Al, and B, where 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 [Here, M １ and M ２ Each of these 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 may be the same or different from each other. M ３ is at least one type of halogen, Here, 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2, and z ≤ 0.

3. ・TiNb ２ O ７－ｚ M ３ ｚ or Li ｗ TiNb ２ O ７－ｚ M ３ ｚ [Here, M ３ [0 ≤ z ≤ 0.3 and 0 ≤ w ≤ 5]; ・Twi １－ｘ Yes ｘ N｡ ２－ｙ M １ ｙ O ７±ｚ , Li ｗ Ti １－ｘ Yes ｘ N｡ ２－ｙ M １ ｙ O ７±ｚ 、Ti １－ｘ Yes ｘ N｡ ２－ｙ M １ ｙ O ７±ｚ , Li ｗ Ti １－ｘ Yes ｘ N｡ ２－ｙ M １ ｙ O ７±ｚ [here, M １ is at least one element selected from the group consisting of Nb, V, Ta, Fe, Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs, and Sn; 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2, and z ≤ 0.

3. ・) １－ｘ e ｘ b ２－ｙ * １ ｙ . ７－ｚ * ２ ｚ 、i ｗ () １－ｘ e ｘ b ２－ｙ * １ ｙ . ７－ｚ * ２ ｚ 、() １－ｘ 5 ｘ b ２－ｙ * １ ｙ . ７－ｚ * ２ ｚ 、i ｗ () １－ｘ 5 ｘ b ２－ｙ * １ ｙ . ７－ｚ * ２ ｚ [ここで、 M １ and M ２ Each of these 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 may be the same or different from each other. Here, 0 ≤ w ≤ 5, 0 ≤ x ≤ 1, 0 ≤ y ≤ 2, and z ≤ 0.

3. Selected from the group consisting of; -TiO ２ ;TiO ｘ N ｙ (x < 2 and 0 < y < 0.2); -LiSiTON, tin-silicon oxynitride, more specifically, formula SiSn ０．８７ O １．２０ N １．７２ , and its lithium-ionized form; - MO ｘ N ｙ Nitrides and oxynitrides of type [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, x ≥ 0 and y ≥ 0.3]; -Li ３－Ｘ M ｘ N (where M is at least one element selected from Cu, Ni, and 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 iron phosphate (generally formula LiFePO) ４ (represented by); - Typical Si ａ Sn ｂ O ｙ N ｚ A mixed silicon and tin oxynitride represented by (a>0, b>0, a+b≦2, 0<y≦4, 0<z≦3), also called SiTON, and especially SiSn ０．８７ O １．２ N １．７２ Also, a typical formula is Si ａ Sn ｂ C ｃ O ｙ Oxynitride carbides such that Nz (a > 0, b > 0, a + b ≤ 2, 0 < c < 10, 0 < y < 24, 0 < z < 17); -Si ｘ N ｙ Nitrides of the type (especially x=3 and y=4), Sn ｘ N ｙ Nitrides of the type (especially x=3 and y=4), Zn ｘ N ｙ Nitrides of the type (especially x=3 and y=2); Li ３－ｘ M ｘ N-type nitride (0 ≤ x ≤ 0.5 if M = Co, 0 ≤ x ≤ 0.6 if M = Ni, 0 ≤ x ≤ 0.3 if M = Cu); Si ３－ｘ M ｘ N ４ (M = Co or Fe, and 0 ≤ x ≤ 3), - SnO oxide ２ , SnO, Li ２ SnO ３ SnSiO ３ Li ｘ SiO ｙ (x >= 0 and 2 > y > 0), Li ４ Ti ５ O １２ TiNb ２ O ７ Co ３ O ４ SnB ０．６ P ０．４ O ２．９ and TiO ２ ; -Si, Sn, SiO ２ , SnO ２ , SiN, SnN, and mixtures thereof; -TiNb containing 0% to 10% by mass of carbon ２ O ７ A composite oxide, wherein carbon is preferably selected from graphene and carbon nanotubes; Selected from group (D) consisting of, or - Alloys based on Si, Ge, Sn, Sb, Bi, and P, and alloys of various compounds thereof. -MXenes. MXenes is M ｎ＋１ X ｎ T ｘ This is a class of two-dimensional materials with a stoichiometry of type 1, where M is a transition metal, preferably selected from Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, and W. X is selected from C and / or N, and T is F, Cl, I, Br, O, S, Se, Te, OH, and NH. ２ A surface endpoint selected from, where 1 ≤ n ≤ 4, - Conversion type anode material, for example G ２ Ti ３ O ７、 G ４ Ti ５ O １２、 GTi ２ (PO ４ ) ３ (G is an oxide of Na or K) The following elements Si, Ge, Sn, Sb, Bi and their alloys: oxides, sulfides, selenides, phosphides, A method for manufacturing a porous electrode according to any one of claims 1 to 9, characterized in that it belongs to group (E) consisting of the following.

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 an electrical energy storage or generation device, using a method for manufacturing a porous electrode according to any one of claims 1 to 11, or using a porous electrode according to claim 12.

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

15. The method according to claim 14, wherein the apparatus is a lithium-ion battery, the method for manufacturing a porous electrode according to claim 10 is carried out to manufacture a positive electrode having the electrode active material P selected from group (A), or the method according to claim 11 is carried out to manufacture a negative electrode having the electrode active material P selected from group (D).

16. The method according to claim 14, wherein the apparatus is a sodium-ion battery, the method for manufacturing a porous electrode according to claim 10 is carried out to manufacture a positive electrode having an electrode active material P selected from group (B), or the method according to claim 11 is carried out to manufacture a negative electrode having an electrode active material P selected from group (E).

17. The apparatus is a potassium-ion battery, the method for manufacturing a porous electrode according to claim 10 is carried out to manufacture a positive electrode having an electrode active material P selected from group (C), or the method according to claim 11 is carried out to manufacture a negative electrode having an electrode active material P selected from group (E), according to claim 14.

18. The device is a lithium-ion battery, a sodium-ion battery, or a potassium-ion battery, and the porous electrode is preferably composed of an electrolyte. - An electrolyte comprising at least one aprotic solvent and at least one lithium salt, sodium salt, or potassium salt; - An electrolyte comprising 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 salt of lithium, sodium, or potassium; - Ionic liquid polymer; - A polymer made into an ion conductor by adding at least one lithium salt, sodium salt, or potassium salt; and - A polymer made into an ion conductor by adding a liquid electrolyte to either the polymer phase or the porous structure of the porous electrode, or by an ion-conducting polymer, preferably an ion-conducting polymer 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); The method according to any one of claims 13 to 17, characterized in that it is impregnated with a phase supporting lithium ions, sodium ions, or potassium ions, selected from the group consisting of the above.

19. An electrical energy storage or generating apparatus that can be obtained by the method described in any one of claims 13 to 18.

20. The electrical energy storage or generation apparatus according to claim 19, characterized in that it 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.

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