Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/32—Manganese, technetium or rhenium
  • B01J23/34—Manganese
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/04—Sulfides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
  • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
  • B01J27/198—Vanadium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/24—Nitrogen compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
  • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/33—Electric or magnetic properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0215—Coating
  • B01J37/0221—Coating of particles
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D13/00—Electrophoretic coating characterised by the process
  • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
  • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0438—Processes of manufacture in general by electrochemical processing
  • H01M4/045—Electrochemical coating; Electrochemical impregnation
  • H01M4/0457—Electrochemical coating; Electrochemical impregnation from dispersions or suspensions; Electrophoresis
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
  • H01M50/491—Porosity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to the manufacture of dense layers, usable as a layer of electrodes or electrolytes in electrchemical devices and multi-layer batteries, such as lithium ion batteries. More specifically, the invention relates to a new process for manufacturing these dense layers from inorganic nanoparticles, which may optionally have received functionalization with an organic coating layer, which may be polymeric. The invention also relates to multi-layer batteries incorporating at least one dense layer obtained by this method, this layer being able in particular to act as an electrode in a lithium ion battery.
• the invention also relates to a new method of manufacturing lithium ion batteries, in which at least one dense electrode layer is deposited using the new dense layer manufacturing method, and in which a layer is also deposited. porous.
• the ideal battery for powering autonomous electrical devices such as: telephones and laptops, portable tools, autonomous sensors
• for the traction of electric vehicles would have a high lifespan, would be able to store both large quantities of energy and power, and would not present a risk of overheating or even explosion.
• lithium ion batteries which have the best energy density among the various storage technologies offered.
• the manufacturing processes of lithium ion batteries are presented in numerous articles and patents, and the book “Advances in Lithium-Ion Batteries” (ed. W. van Schalkwijk and B. Scrosati), published in 2002 (Kluever internationale) / Plénum Publishers) gives a good overview.
• the electrodes of lithium ion batteries can be manufactured using coating techniques (in particular: roller coating (in English “roll coating”), doctor blade coating (in English “doctor blade”), strip casting (in English “tape casting”), coating through a slot-shaped die (in English "slot-die”)).
• coating techniques in particular: roller coating (in English “roll coating”), doctor blade coating (in English “doctor blade”), strip casting (in English “tape casting”), coating through a slot-shaped die (in English “slot-die”).
• the active materials used to make the electrodes are in the form powders with an average particle size between 5 and 15 ⁇ m in diameter. These particles are integrated into an ink which consists of these particles and deposited on the surface of a substrate.
• the inks (or pastes) deposited to form the electrodes contain particles of active materials, but also (organic) binders, carbon powder to ensure electrical contact between the particles, and solvents which are evaporated during the step of drying the electrodes.
• a calendering step is carried out on the electrodes. After this compression step, the active particles of the electrodes occupy approximately 60% of the volume of the deposit, which means that there generally remains 40% of porosities between the particles.
• the contact between each of the particles is essentially point-like and the structure of the electrode is porous.
• the porosities are filled with an electrolyte, which can be liquid (aprotic solvent in which a lithium salt is dissolved) or in the form of a more or less polymerized gel impregnated with a lithium salt. Since the thickness of the electrodes of lithium ion batteries is generally between 50 ⁇ m and 400 ⁇ m, the transport of lithium ions in the thickness of the electrode takes place via the porosities which are filled with electrolyte (containing lithium salts). Depending on the quantity and size of the porosities, the rate of diffusion of lithium in the thickness of the electrode varies.
• lithium ions must diffuse both in the thickness of the particle and in the thickness of the electrode. Diffusion within the particle of active material is slower than in the electrolyte with which the porous electrode is impregnated: this electrolyte is liquid or gelled. The slow diffusion within the electrode particles contributes to the series resistance of the battery. Also, to achieve good battery power, the particle size must be reduced; in standard lithium ion batteries it is typically between 5 ⁇ m and 15 ⁇ m.
• the power and energy of the battery can be modulated depending on the thickness of the layers, the size and density of active particles contained in the ink, the power and energy of the battery can be modulated.
• the increase in energy density necessarily comes at the expense of power density.
• the high power battery cells must use electrodes and separators of small thickness and high porosity, while the increase On the contrary, energy density requires increasing these same thicknesses and reducing the porosity rate.
• the porosities of the electrodes must be filled with electrolyte. This filling is only possible if these porosities are open.
• impregnation of the electrode with the electrolyte may become very difficult, if not impossible.
• the rate of porosity, impregnated with electrolyte decreases, the electrical resistance of the layer decreases and its ionic resistance increases.
• the porosity drops below 30% or even 20%, the ionic resistance increases sharply because certain porosities are then liable to close, which prevents wetting of the electrode by the electrolyte.
• the thickness of these films is appropriate to limit the thickness of these films to less than 50 ⁇ m, and preferably to less than 25 ⁇ m. ⁇ m, in order to allow the rapid diffusion of lithium ions in the solid, without loss of power.
• the main route used consists in depositing by a vacuum process a film of lithium insertion electrode material. This technique makes it possible to obtain dense films, without porosities or binders, and consequently having excellent energy densities, and good temperature resistance.
• PVD deposition Physical Vapor Deposition
• PVD deposition is the technology most currently used for the manufacture of thin film microbatteries. Indeed, these products require films free of porosities and other point defects to guarantee a low electrical resistivity, and the good ionic conduction necessary for the good functioning of the electrochemical devices.
• the deposition rate obtained with such technologies is of the order of 0.1 ⁇ m to 1 ⁇ m per hour.
• PVD deposition techniques make it possible to obtain films of very good quality, containing hardly any point defects, and make it possible to carry out deposits at relatively low temperatures.
• Due to the difference in evaporation rate between the different elements it is difficult to deposit complex compounds with such techniques, and to control the stoichiometry of the layer.
• This technique is perfectly suited to the production of thin layers of simple chemical composition, but as soon as one seeks to increase the deposition thickness, the deposition time becomes too long to consider industrial use in the field of low-cost products. .
• the other technologies currently available for producing dense ceramic films include embodiments based on the densification of compact deposits of particles or else obtaining a film by sol-gel type techniques.
• the sol-gel techniques consist in depositing on the surface of a substrate a polymeric network obtained after stages of hydrolysis, polymerization and condensation. The sol-gel transition appears during the evaporation of the solvent which accelerates the reaction processes at the surface. This technique makes it possible to produce compact deposits of very small thickness.
• the films thus obtained have a thickness of the order of a hundred nanometers. These thicknesses are then too small to allow reasonable energy storage in battery applications.
• the metallic films used to collect the current on these electrodes are also deposited by inking techniques.
• the metallic powders will also be sintered at the same time as the “green-sheet”. In fact, during the sintering step, the porosities between the particles of ceramic material will be filled, which will lead to a shrinkage of the strip.
• the present invention seeks to remedy at least in part the drawbacks of the prior art mentioned above.
• the problem that the present invention seeks to solve is to provide a method for manufacturing dense ceramic layers, directly on a metallic substrate and which is simple, safe, rapid, easy to implement, inexpensive.
• the present invention also aims to produce dense solid (ceramic) layers, which can be used in lithium ion batteries, containing no or very few defects and porosity.
• the present invention also aims to provide dense electrodes and dense electrolytes having high ionic conductivity, stable mechanical structure, good thermal stability and long service life.
• Another aim of the invention is to provide a method of manufacturing an electronic, electrical or electrotechnical device such as a battery, a capacitor, a supercapacitor, a photovoltaic cell comprising a dense electrode or a dense electrolyte according to the invention. .
• the problem is solved by a method of manufacturing a lithium ion battery with a capacity greater than 1 mA h, said method comprising the deposition of at least one dense layer, which may be an anode and / or a cathode and / or an electrolyte, by a method for depositing a dense layer which comprises the steps of: supplying a substrate and a suspension of non-agglomerated nanoparticles of a material P, depositing a layer, on said substrate, from the suspension of primary nanoparticles of a material P; drying of the layer thus obtained, densification of the dried layer by mechanical compression and / or heat treatment, knowing that the drying step and the densification step by can be done at least partially at the same time, or during a temperature ramp.
• Said method which forms a first object of the present invention, is characterized in that the suspension of non-agglomerated nanoparticles of material P comprises nanoparticles of material P having a particular size distribution, making it possible to obtain after deposition a density greater than 75%.
• Said size is characterized by its value of D50.
• the standard deviation / average size ratio of the nanoparticles of material P must be greater than 0.6, and the average size of the primary nanoparticles of material P less or equal to 50 nm; either discontinuously: in this case the size distribution of the nanoparticles of material P comprises nanoparticles with a first size D1 between 50 nm and 20 nm, and nanoparticles with a second size D2 at least five times smaller than that of D1.
• the particles of size D1 represent between 50 and 75% of the total mass of nanoparticles.
• Said suspension of non-agglomerated nanoparticles of material P can be obtained by using a suspension of monodisperse size D1 nanoparticles, and / or said suspension of D2 size nanoparticles can be obtained by using a monodisperse suspension.
• the deposition of the solid and dense ceramic layer is carried out electrophoretically, by the dip coating process, by the inkjet printing process, by roller coating, by through coating. a slot-shaped die, by curtain coating, or by scraping.
• the dried layer After deposition, the dried layer has a density greater than 75%, thanks to the particular size distribution of the nanoparticles which constitute it. This density can be further increased by a step of densifying the dried layer, by mechanical compression and / or by heat treatment.
• a second object of the invention is a dense layer in a battery with a capacity greater than 1 mA h (and preferably a lithium ion battery with a capacity greater than 1 mA h), said dense layer being capable of 'be obtained by the method according to the invention.
• Said dense layer can in particular be an anode layer, a cathode layer and / or an electrolyte layer.
• a third subject of the invention is a lithium ion battery with a capacity greater than 1 mA h, capable of being obtained by this method.
• Said battery therefore comprises at least one dense layer, which may be an anode layer and / or a cathode layer and / or an electrolyte layer.
• This dense anode layer and / or this dense cathode layer may have a thickness of between approximately 1 ⁇ m and approximately 50 ⁇ m.
• said lithium ion battery comprises an anode and a cathode which are dense layers according to the invention.
• the electrolyte layer can also be a dense layer according to the invention.
• said battery comprises a porous separator which separates said anode and said cathode; this porous separator is infiltrated by a liquid electrolyte.
• This electrolyte layer or this separator advantageously has a thickness of between approximately 1 ⁇ m and approximately 25 ⁇ m, and preferably between approximately 3 ⁇ m and approximately 10 ⁇ m.
• the size of a particle is defined by its largest dimension.
• the term “nanoparticle” is understood to mean any particle or object of nanometric size having at least one of its dimensions less than or equal to 100 nm. This size D is expressed here as size D 50 .
• nanoparticle is used herein to denote primary particles, as opposed to particles formed by the aggregation or agglomeration of several primary particles. Such agglomerates can be reduced to nanoparticles (as we understand it here) by a deagglomeration operation, for example by grinding or ultrasonic treatment.
• the density of a layer is here expressed in relative value (for example in percent), which is obtained by the comparison between the real density of the layer (designated here as d layer ) and the theoretical density of the solid material which constitutes it ( referred to here as theoretical d).
• the problem is solved by a method for depositing a layer from a suspension of nanoparticles, in which the size of the nanoparticles has a particle size distribution of a particular type.
• a suspension of nanoparticles which represents a particular size distribution of nanoparticles, so as to significantly increase the density of the deposit of nanoparticles before sintering.
• Obtaining such concentrated suspensions requires the use of stabilizers, which are organic ligands (for example of the PVP type), in order to avoid the phenomena of agglomeration between nanoparticles.
• stabilizers which are organic ligands (for example of the PVP type), in order to avoid the phenomena of agglomeration between nanoparticles.
• These ligands will be removed at the start of the sintering heat treatment: typically, an intermediate heat ramp is produced in order to remove all these organic compounds before sintering.
• the viscosity of the suspension used for the deposition essentially depends on the nature of the liquid phase (solvent), on the size of the particles and on their concentration (expressed by the dry extract).
• the viscosity of the suspension, as well as the parameters of the deposition process determine the thickness of the deposit.
• the viscosity generally used for dip coating, curtain coating or slot die can vary widely and is between approximately 20 cP and approximately 2000 cP, measured at 20 ° C.
• a colloidal suspension intended for depositing is often called an “ink”, regardless of its viscosity.
• the nanoparticles will come into contact and begin the consolidation process.
• the surfaces of the nanoparticles will weld together at the contact points; this phenomenon is known as “necking”.
• these contact points which have become weld zones will increase by diffusion, until they fill the empty spaces left by the initial porosity of the deposit. It is indeed the filling of these voids that is at the origin of the restriction.
• colloidal suspensions of nanoparticles are used, the mean size of the nanoparticles of which does not exceed 100 nm. These nanoparticles also have a fairly wide distribution in size. When this size distribution follows an approximately Gaussian distribution, then the ratio (sigma / R avg ) of the standard deviation over the mean radius of the nanoparticles must be greater than 0.6.
• the mean diameter of the largest distribution should not exceed 100 nm, and preferably not exceed 50 nm.
• This first population of the largest nanoparticles may have a narrower size distribution and with an igma / R avg ratio of less than 0.6.
• This population of “large” nanoparticles should represent between 50% and 75% of the dry extract of the deposit (expressed as a percentage by mass relative to the total mass of nanoparticles in the deposit).
• the second population of nanoparticles will therefore represent between 50% and 25% of the dry extract of the deposit (expressed as a percentage by mass relative to the total mass of nanoparticles in the deposit).
• the average diameter of the particles of this second population must be at least 5 times smaller than that of the population of the largest nanoparticles. As for larger nanoparticles, the size distribution of the second population may be tighter and with potentially a rapportsigma / R mean less than 0.6. It is preferred that the mean diameter of the second population is at least one fifteenth of that of the population of the largest nanoparticles, and preferably at least one twelfth; this facilitates the densification of the layer after its deposition.
• these nanoparticles can advantageously be synthesized in the presence of ligands or organic stabilizers so as to avoid aggregation, or even agglomeration, of the nanoparticles.
• the materials used in the manufacture of lithium ion batteries are particularly sensitive, the slightest modification of their crystalline state or their chemical composition results in degraded electrochemical performance. Also, for this type of application, it is preferable to use nanoparticles prepared in suspension directly by precipitation, according to solvothermal or hydrothermal type processes, at the desired primary nanoparticle size.
• This suspension of bimodal nanoparticles is then used to deposit the compact layers, which will then be densified by a heat treatment at low temperature and can be used in particular as electrodes or electrolyte in electrochemical devices such as for example lithium ion batteries.
• Different processes can be used to deposit these layers, and in particular electrophoresis, inkjet printing (called “ink-jet”), scraping (called “doctor blade”), coating.
• roller coating (called “roll coating” in English), curtain coating (called “curtain coating” in English), coating by dipping (called in English “dip-coating”), deposits by slot-die.
• Electrophoresis allows a uniform layer to be deposited over large areas with a high deposition rate. Coating techniques, in particular by dipping, roller, curtain or scraping, make it possible to simplify the management of the baths with respect to electrophoresis, since the composition of the bath remains constant during the deposition by coating. Inkjet printing deposition allows localized deposits to be made. Dense electrodes and electrolytes in a thick layer and produced in a single step can be obtained by the aforementioned methods from a suspension of bimodal or polydisperse nanoparticles.
• the method according to the invention makes it possible to manufacture dense layers having a density of at least 90% of the theoretical density, preferably at least 95% of the theoretical density, and even more preferably at least 96% of the theoretical density, and optimally at least 97% of the theoretical density, knowing that the remainder consists of residual porosity, which consists of closed pores.
• the substrate serving as a current collector in batteries employing dense electrodes according to the invention is metallic, for example a metallic foil. It must be selected so as to withstand the temperature of a possible thermal or thermomechanical treatment which will be applied to the layer deposited on this substrate, and this temperature will depend on the chemical nature of said layer.
• the substrate is preferably chosen from strips of titanium, molybdenum, chromium, tungsten, copper, nickel or stainless steel or any alloy containing at least one of the preceding elements.
• the metal foil can be coated with a layer of noble metal, in particular chosen from gold, platinum, palladium, titanium, molybdenum, tungsten, chromium or alloys mainly containing at least one or more of these metals, or a layer of conductive material of ITO type (which has the advantage of also acting as a diffusion barrier).
• a layer of noble metal in particular chosen from gold, platinum, palladium, titanium, molybdenum, tungsten, chromium or alloys mainly containing at least one or more of these metals, or a layer of conductive material of ITO type (which has the advantage of also acting as a diffusion barrier).
• this electrode layer can be deposited either on a metallic surface of the current collector, or on another inorganic, dense or porous layer, for example on a dense electrolyte layer or on a porous separator.
• Bimodal nanoparticles can be deposited by the dip coating process, regardless of the chemical nature of the nanoparticles used; of course, the other deposition etchniques indicated above can also be used.
• nanoparticles are mixed, deagglomerated by ultrasound, with 70% by mass of 30 nm particles and 30% by mass of 5 nm nanoparticles in an ink with 15% overall dry extract, in ethanol and containing PVP as stabilizing.
• Each dipping pass produces only a layer of fairly limited thickness; the wet layer must be dried.
• the step of deposition by dipping followed by the step of drying the layer can be repeated as much as necessary.
• this succession of dipping / drying coating steps is time-consuming, the dip-coating deposition process is a simple, safe process, easy to implement, to industrialize and to obtain a homogeneous final layer and compact.
• the layers deposited by soaking must be dried. Once dried, a heat treatment is carried out in two stages. First, the deposit is maintained for 10 minutes at 400 ° C in order to calcine all the organic compounds it contains. Then the treatment temperature rose to 550 ° C. and maintained for one hour at this temperature in order to obtain consolidation of the deposit.
• the selection of the materials of the nanoparticles obviously depends on the function of the layers thus deposited in the targeted electrochemical, electrical or electronic device.
• the nanoparticles used in the present invention are inorganic and non-metallic, knowing that they can be coated with an organic functionalization layer (“core-shell” type particles); this will be described below. These particles coated with an organic layer are included here in the term “inorganic particles”.
• LiFePO 4 , LiMnPO 4 , LiCoPO 4 , LiNiPO 4 , Li 3 V 2 (RO 4 ) 3 ; phosphates of formula LiMM'PO 4 , with M and M '(M 1 M') selected from Fe, Mn, Ni, Co, V; all lithiated forms of the following chalcogenides: V 2 O 5 , V 3 O 8 , TiS 2 , titanium oxysulphides (TiO y S z with z 2-y and 0.3 ⁇ y ⁇ 1), tungsten oxysulphides (WO y S z with 0.6 ⁇ y ⁇ 3 and 0.1 ⁇ z ⁇ 2), CuS, CuS 2 , preferably Li x V 2 O 5 with 0 ⁇ x ⁇ 2, Li x V308 with 0 ⁇ x ⁇ 1.7 , Li x TiS 2 with 0 ⁇ x ⁇ 1, the Li x TiO y S z with z
• the layer according to the invention must function as the anode of a battery, especially of a lithium ion battery, it can be made for example from a material P which is an anode material chosen from among : carbon nanotubes, graphene, graphite; lithiated iron phosphate (of typical formula LiFePO4); mixed silicon and tin oxynitrides (of typical formula Si a Sn b O y N z with a> 0, b> 0, a + b ⁇ 2, 0 ⁇ y ⁇ 4, 0 ⁇ z ⁇ 3) (also called SiTON ), and in particular SiSn 0.87 O 1.2 N 1.72 ; as well as oxynitride-carbides of typical formula Si a Sn b C c O y N z with a> 0, b> 0, a + b ⁇ 2, 0 ⁇ c ⁇ 10, 0 ⁇ y ⁇ 24, 0 ⁇ z ⁇ 17; nitrides of the Si x N y type
• the oxides SnO 2 , SnO, Li 2 SnO 3 , SnSiO 3 , Li x SiO y (x> 0 and 2>y> 0), Li 4 Ti 5 O 12 , TiNb207, Co 3 O 4 , SnB o, 6 P o, 4 O 2,9 and TiO 2 , the composite oxides TiNlb 2 O 7 comprising between 0% and 10% by mass of carbon, preferably the carbon being chosen from graphene and carbon nanotubes, the compounds of formula general Li w Ti 1-x M 1 x Nb 2-y M 2 y O 7-z M 3 z in which M 1 and M 2 are each at least one element selected from the group consisting of Nb, V, Ta, Fe , Co, Ti, Bi, Sb, As, P, Cr, Mo, W, B, Na, Mg, Ca, Ba, Pb, Al, Zr, Si, Sr, K, Cs and Sn, M 1 and M 2 which may be identical or different from
• the layer according to the invention is to function as an electrolyte in a battery, especially of a lithium ion battery, it can be produced for example from a material P which is an electrolyte material chosen from: garnets of formula Li d A 1 x A 2 y (TO 4 ) z where A 1 represents a cation of oxidation degree + II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and where A 2 represents a cation of oxidation degree + III, preferably Al, Fe, Cr, Ga, Ti, La; and where (TO 4 ) represents an anion in which T is an atom of oxidation degree + IV, located at the center of a tetrahedron formed by oxygen atoms, and in which TO 4 advantageously represents the silicate anion or zirconate, knowing that all or part of the T elements of an oxidation degree + IV can be replaced by atoms of an oxidation degree + III or + V, such as Al
• coated nanoparticles of the "core - bark” type
• the nanoparticles used in the inks used to make these deposits intended for the electrodes can also have a core-shell structure.
• the performance of the dense electrodes thus obtained will depend on their property of ionic and electronic conduction.
• the heart is formed from an electrode material (anode or cathode), and the shell is formed from a material which is both an electronic conductor and which does not prevent the passage.
• lithium ions can be formed by a layer of a metal, which is thin enough to allow lithium ions to pass, or by a sufficiently thin layer of graphite, or by a layer of an ionic conductor. which is also a good electronic conductor.
• the core of the nanoparticles used in the method according to the invention is formed from an electrolyte material, and the shell is formed from an inorganic or organic material which is a good conductor of ions, in particular lithium ions, and which must be a good electronic insulator.
• this layer is made of a polymer material.
• a polymer layer has, among other things, the advantage of being malleable, which facilitates the compacting of the layer deposited from these particles.
• This process called here “functionalization” of the inorganic nanoparticles forming the core by a shell, consists in grafting to the surface of the nanoparticles a molecule having a structure of the Q-Z type in which Q is a function ensuring the attachment of the molecule to the surface, and Z is preferably a PEO group.
• a complexing function of the surface cations of the nanoparticles can be used, such as the phosphate or phosphonate function.
• the inorganic nanoparticles are functionalized with a PEO derivative of the type where X represents an alkyl chain or a hydrogen atom, n is between 40 and 10,000 (preferably between 50 and 200), m is between 0 and 10, and
• Q ' is an embodiment of Q and represents a group selected from the group formed by: and where R represents an alkyl chain or a hydrogen atom, R 'represents a methyl group or an ethyl group, x is between 1 and 5, and x' is between 1 and 5.
• the inorganic nanoparticles are functionalized with methoxy-PEO-phosphonate where n is between 40 and 10,000 and preferably between 50 and 200.
• a solution of QZ (or Q'-Z, where appropriate) is added to a colloidal suspension of nanoparticles of electrolyte or of electronic insulator so as to obtain a molar ratio between Q (which comprises here Q ') and the set of cations present in the inorganic nanoparticles (here abbreviated “NP-C”) between 1 and 0.01, preferably between 0.1 and 0.02.
• Q which comprises here Q '
• NP-C the set of cations present in the inorganic nanoparticles
• the functionalization of the inorganic electronic nanoparticles by the QZ molecule risks inducing steric hindrance such that said nanoparticles cannot be completely functionalized; it also depends on the size of the nanoparticles.
• the QZ molecule risks not being in sufficient quantity to ensure sufficient conductivity of the lithium ions; it also depends on the particle size. Using a greater amount of QZ during functionalization would result in unnecessary consumption of QZ.
• a colloidal suspension of inorganic nanoparticles at a mass concentration of between 0.1% and 50%, preferably between 5% and 25%, and even more preferably at 10% is used to carry out the functionalization of the inorganic nanoparticles.
• the inorganic nanoparticles are dispersed in a liquid phase such as water or ethanol.
• This reaction can be carried out in any suitable solvent making it possible to solubilize the Q-Z molecule.
• the functionalization conditions can be optimized, in particular by adjusting the temperature and the duration of the reaction, and the solvent used.
• the reaction medium After adding a QZ solution to a colloidal suspension of electrolyte nanoparticles, the reaction medium is left under stirring for 0 h to 24 hours (preferably for 5 minutes to 12 hours, and even more preferably for 0.5 hours to 2 hours). hours), so that at least some, preferably all of the QZ molecules can be grafted to the surface of the inorganic nanoparticles.
• the functionalization can be carried out under heating, preferably at a temperature between 20 ° C and 100 ° C. The temperature of the reaction medium must be adapted to the choice of the functionalizing molecule Q-Z.
• These functionalized nanoparticles therefore have a core (“core”) made of inorganic material and a shell made of PEO.
• the thickness of the bark can typically be between 1 nm and 100 nm; this thickness can be determined by transmission electron microscopy after labeling the polymer with ruthenium oxide (RuO 4 ).
• the nanoparticles thus functionalized are then purified by cycles of successive centrifugations and redispersions and / or by tangential filtration. After redispersion of the functionalized inorganic nanoparticles, the suspension can be reconcentrated until the desired dry extract is reached, by any suitable means.
• the dry extract of a suspension of inorganic nanoparticles functionalized with PEO comprises more than 40% (by volume) of solid electrolyte material, preferably more than 60% and even more preferably more than 70% of solid electrolyte material. solid electrolyte.
• Densification of the layer produced with nanoparticles of organic core-shell type after its deposition can be carried out by any suitable means, preferably: a) by any mechanical means, in particular by mechanical compression, preferably uniaxial compression; b) by thermocompression, i.e. by heat treatment under pressure.
• the optimum temperature strongly depends on the chemical composition of the deposited materials, it also depends on the particle sizes and the compactness of the layer.
• a controlled atmosphere is preferably maintained in order to avoid oxidation and surface pollution of the deposited particles.
• the compaction is carried out under a controlled atmosphere and at temperatures between room temperature and the melting temperature of the polymer (typically PEO) used; the thermocompression can be carried out at a temperature between room temperature (about 20 ° C) and about 300 ° C; but it is preferred not to exceed 200 ° C. (or even more preferably 100 ° C.) in order to avoid degradation of the PEO.
• the polymer typically PEO
• the thermocompression can be carried out at a temperature between room temperature (about 20 ° C) and about 300 ° C; but it is preferred not to exceed 200 ° C. (or even more preferably 100 ° C.) in order to avoid degradation of the PEO.
• one of the advantages of organic bark is the malleability of the bark; PEO, for example, is an easily deformable polymer at relatively low pressure.
• PEO for example, is an easily deformable polymer at relatively low pressure.
• the densification of the electrolyte or electronic insulator nanoparticles functionalized by a polymer such as PEO can be obtained only by mechanical compression (application of mechanical pressure).
• the compression is carried out in a pressure range of between 10 MPa and 500 MPa, preferably between 50 MPa and 200 MPa and at a temperature of the order of 20 ° C to 200 ° C.
• PEO is amorphous and ensures good ionic contact between the solid electrolyte particles. PEO can thus conduct lithium ions, even in the absence of liquid electrolyte; the PEO is at the same time an electronic insulator. It promotes the assembly of the lithium ion battery at low temperature, thus limiting the risk of interdiffusion at the interfaces between the electrolytes and the electrodes.
• the electrolyte layer obtained after densification may have a thickness less than 10 ⁇ m, preferably less than 6 ⁇ m, of preferably less than 5 ⁇ m, in order to limit the thickness and the weight of the battery without reducing its properties.
• the method according to the invention makes it possible to deposit dense inorganic layers in lithium ion batteries with a capacity greater than 1 mA h.
• said dense layers can perform the function of an anode or of a cathode or of an electrode
• the battery can comprise several dense inorganic layers according to the invention.
• These batteries can be of the “all solid” type, the dense layers exhibiting only a very low porosity.
• the battery also comprises at least one porous inorganic layer.
• the “porous inorganic layer”, preferably mesoporous, can be deposited by a process preferably selected from the group formed by: electrophoresis, a printing process, preferably chosen from among inkjet printing and flexographic printing, and a coating process, preferably selected from roll coating, curtain coating, scrap coating, die-extrusion coating slit-shaped, coating by dipping, and this from a suspension of aggregates or agglomerates of nanoparticles, preferably from a concentrated suspension containing agglomerates of nanoparticles.
• a colloidal suspension comprising aggregates or agglomerates of nanoparticles of at least one inorganic material, with an average primary diameter D50 of between 2 nm and 100 nm, preferably between 2 nm and 60 nm, said aggregates or agglomerates typically having an average diameter D50 of between 50 nm and 300 nm (preferably between 100 nm and 200 nm).
• the layer thus obtained is then dried and the layer is consolidated, by pressing and / or heating, to obtain a porous layer, preferably mesoporous and inorganic. This process is particularly advantageous with nanoparticles formed from electrolyte materials.
• the mesoporous layer can be deposited on a dense layer deposited by the method according to the invention, or said dense layer is deposited on said mesoporous layer prepared by the method which has just been described.
• said porous separator layer In order for said porous separator layer to be able to fulfill its function of electrolyte, it must be impregnated with a liquid carrying mobile cations; in the case of a lithium ion battery, this cation is a lithium cation.
• This phase carrying lithium ions is preferably selected from the group formed by: o an electrolyte composed of at least one aprotic solvent and at least one lithium salt; o an electrolyte composed of at least one ionic liquid or ionic polyliquid and at least one lithium salt; o a mixture of at least one aprotic solvent and at least one ionic liquid or ionic polyliquid and at least one lithium salt; o a polymer made ionic conductive by adding at least one lithium salt; and o a polymer rendered ionic conductive by the addition of a liquid electrolyte, either in the polymer phase or in the mesoporous structure, said polymer preferably being selected from the group formed by poly (ethylene oxide), poly ( propylene oxide), polydimethylsiloxane, polyacrylonitrile, poly (methyl methacrylate), poly (vinyl chloride), poly (vinylidene fluoride), PVDF-hexafluoropropylene.
• a suspension of Li 3 PO 4 nanoparticles was prepared from the two solutions presented below: First, 45.76 g of CH3COOLi, 2H 2 O were dissolved in 448 ml of water, then 224 ml of ethanol were added with vigorous stirring to the medium in order to obtain a solution A. Second, 16.24 g of H 3 PO 4 (85 wt% in water) were diluted in 422.4 ml of water, then 182 4 ml of ethanol were added to this solution in order to obtain a second solution hereinafter called solution B. Solution B was then added, under stirring vacuum, to solution A.
• the reaction medium was homogenized for 5 minutes then was kept for 10 minutes with magnetic stirring. It was allowed to settle for 1 to 2 hours. The supernatant was discarded and then the remaining suspension was centrifuged for 10 minutes at 6000 g. Then 1.2 l of water were added to resuspend the precipitate (use of a sonotrode, magnetic stirring). Two additional washes of this type were then carried out with ethanol. With vigorous stirring, 15 ml of a solution of Bis (2- (methacryloyoloxy) ethyl) phosphate at 1 g / ml were added to the colloidal suspension in ethanol thus obtained. The suspension has thus become more stable. The suspension was then sonicated using a sonotrode.
• the suspension was then centrifuged for 10 minutes at 6000 g.
• the pellet was then redispersed in 1.2 l of ethanol and then centrifuged for 10 minutes at 6000 g.
• the pellets thus obtained are redispersed in 900 ml of ethanol in order to obtain a 15 g / l suspension suitable for carrying out an electrophoretic deposit.
• Agglomerates of about 200 nm consisting of primary Li 3 PO 4 particles of 10 nm were thus obtained in suspension in ethanol.
• Thin porous Li 3 PO 4 layers were then deposited by electrophoresis on the surface of the anodes and cathodes previously produced by applying an electric field of 20V / cm to the suspension of Li 3 PO 4 nanoparticles obtained previously, for 90 seconds to obtain a layer of approximately 2 ⁇ m.
• the layer was then dried in air at 120 ° C. and then a calcination treatment at 350 ° C. for 120 minutes was carried out on this previously dried layer in order to remove all traces of organic residues.
• the two subsystems were stacked so that the Li 3 PO 4 films are in contact.
• This stack was then hot pressed under vacuum between two flat plates. To do this, the stack was first placed under a pressure of 5 MPa and then dried under vacuum for 30 minutes at 10 -3 bars. The press platens were then heated to 550 ° C with a rate of 0.4 ° C / second. At 550 ° C, the stack was then thermo-pressed under a pressure of 45 MPa for 20 minutes, then the system was cooled to room temperature.
• Impregnation of the separator with a liquid electrolyte This assembly was then impregnated, under an anhydrous atmosphere, by soaking in an electrolytic solution comprising PYR14TFSI, and LiTFSI at 0.7 M.
• PYR14TFSI is the common abbreviation of 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide.
• LITFSI is the common abbreviation for lithium bis-trifluoromethanesulfonimide (CAS RN 90076-65-6).
• the ionic liquid instantly enters by capillary action into the pores of the separator. Each of the two ends of the system was kept immersed for 5 minutes in a drop of the electrolyte mixture.
• the impregnation is carried out after the encapsulation of the battery, and followed by the production of the electrical contact members.
• the battery according to the invention can be a mini-battery, the capacity of which is greater than 1 mAh and up to approximately 1 Ah, or a battery whose capacity is greater than 1 Ah.
• the method according to the invention lends itself particularly well to the production of layers with a thickness greater than 1 ⁇ m, or even greater than 5 ⁇ m, while ensuring a low series resistance of the battery.
• a first aspect of the invention is a method of manufacturing a dense layer, which comprises the steps of: - Supply of a substrate and a suspension of non-agglomerated nanoparticles of an inorganic material P;
• said method being characterized in that said suspension of non-agglomerated nanoparticles of material P comprises nanoparticles of material P having a size distribution, said size being characterized by its value of D50, such that: the distribution comprises nanoparticles of material P d 'a first size D1 of between 20 nm and 50 nm, and nanoparticles of material P of a second size D2 characterized by a D50 value at least five times lower than that of D1.
• the distribution has an average size of the material P nanoparticles of less than 50 nm, and a standard deviation to average size ratio greater than 0.6.
• said suspension of non-agglomerated nanoparticles of material P comprises nanoparticles of material P of a first size D1 of between 20 nm and 50 nm, and nanoparticles of material P of a second size D2 characterized by a D50 value at least five times lower than that of D1, and said particles of size D1 represent between 50 and 75% of the total mass of nanoparticles.
• the mean diameter of the second population is at least one fifteenth of that of the first population of nanoparticles, and preferably at least one twelfth.
• said suspension of non-agglomerated nanoparticles of material P is obtained by using a suspension of monodisperse size D1 nanoparticles.
• the suspension of nanoparticles of size D2 is obtained by using a monodisperse suspension.
• this first aspect which is also compatible with its first, second and third variant, a mixture of two populations of nanoparticle sizes is used, so that the average diameter of the largest distribution does not exceed 100 nm, and preferably does not exceed 50 nm.
• this first population of the largest nanoparticles has a size distribution characterized by a sigma / R avg ratio of less than 0.6.
• said population of largest nanoparticles represents between 50% and 75% of the dry extract of the deposit
• the second population of nanoparticles represents between 50% and 25% of the dry extract of the deposit (these percentages being expressed as a percentage by mass relative to the total mass of nanoparticles in the deposit).
• the average diameter of the particles of this second population is at least 5 times smaller than that of the first population of nanoparticles, and preferably the average diameter of the second population is at least one fifteenth of that of the first population of nanoparticles, and preferably at least one twelfth.
• this second population has a size distribution characterized by a sigrna / Rmoy ratio of less than 0.6.
• a process selected from printing techniques in particular by inkjet or inkjet, is used for the deposition of said dense layer.
• printing techniques in particular by inkjet or inkjet
• coating techniques in particular roller, curtain, scraping, dipping, extrusion through a slot.
• said suspension has a viscosity, measured at 20 ° C., between 20 cP and 2000 cP.
• said material P is an inorganic material, preferably selected from the group formed by:
• the oxides SnO 2 , SnO, Li 2 SnO 3 , SnSiO 3 , Li x SiO y (x> 0 and 2>y> 0), Li 4 Ti 5 O 12 , TiNb2O7, Co 3 O 4 , SnB 0, 6P 0.4 O 2 , 9 and TiO 2 , the composite oxides TiNb2O7 comprising between 0% and 10% by weight of carbon, preferably the carbon being chosen from graphene and carbon nanotubes; electrolyte materials, preferably selected from the group formed by: garnets of formula Li d A 1 x A 2 y (TO 4 ) z where A 1 represents a cation of oxidation degree + II, preferably Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and where A 2 represents a cation of oxidation degree + III, preferably Al, Fe, Cr, Ga, Ti, La; and where (TO 4 ) represents an anion in
• LiPON lithium oxynitride and phosphorus
• said nanoparticles of an inorganic material P comprise nanoparticles composed of a core and a shell, the core being formed from said inorganic material P, while the shell is formed from another material, which is preferably organic, and even more preferably polymeric.
• said shell is formed of a material which is an electronic conductor.
• said shell is formed of a material which is an electronic insulator and a cation conductor, in particular a lithium ion conductor.
• said shell is formed of a material which is an electronic conductor and a cation conductor, in particular a lithium ion conductor.
• said nanoparticles of an inorganic material P (or, in the case of the eighth variant , said core of inorganic material P of said nanoparticles) were prepared in suspension by precipitation.
• a second aspect of the invention is a method of manufacturing at least one dense layer in a lithium ion battery with a capacity greater than 1 mA h, said method of manufacturing said dense layer being that according to the first aspect. of the invention, with all the variants and all the sub-variants stated in relation to this first aspect of the invention.
• said material P is selected so that said dense layer can function as an anode in a lithium ion battery.
• said material P is selected so that said dense layer can function as a cathode in a lithium ion battery.
• said material P is selected so that said dense layer can function as an electrolyte in a lithium ion battery.
• a third aspect of the invention is a method of manufacturing at least one dense layer in a lithium ion battery with a capacity greater than 1 mA h, said dense layer being capable of being obtained by the method according to first aspect of the invention, with all the variants and all the sub-variants stated in relation to this first aspect of the invention.
• said material P is selected so that said dense layer can function as an anode in a lithium ion battery.
• said material P is selected so that said dense layer can function as a cathode in a lithium ion battery.
• said material P is selected so that said dense layer can function as an electrolyte in a lithium ion battery.
• a fourth aspect of the invention is a method of manufacturing a lithium ion battery with a capacity greater than 1 mA h, said battery comprising at least one dense electrode layer deposited by the method according to the first aspect of the invention, with all the variants and all the sub-variants stated in relation to this first aspect of the invention, and in which a porous layer intended to form the separator is also deposited, preferably using an electrolyte material according to the seventh variant of the first aspect of the invention.
• said porous layer is a mesoporous layer, preferably with a mesoporous volume of between 25% and 75%, and even more preferably between 30% and 60%.
• the method for depositing said said porous layer is a method preferably selected from the group formed by: electrophoresis, a printing method, chosen preferably from inkjet printing and flexographic printing, and a coating process, preferably selected from roller coating, curtain coating, scrap coating, spray coating. extrusion through a slot-shaped die, coating by dipping, knowing that in all these cases, the deposition is done from a suspension of aggregates or agglomerates of nanoparticles.
• a concentrated suspension containing agglomerates of nanoparticles is used for the deposition of said porous layer.
• a colloidal suspension comprising aggregates or agglomerates of nanoparticles of at least one inorganic material is used for the deposition of said porous layer, with an average primary diameter D50 of between 2 nm and 100 nm, preferably between 2 nm and 60 nm, said aggregates or agglomerates typically having an average diameter D50 of between 50 nm and 300 nm, and preferably between 100 nm and 200 nm.
• said layer thus obtained is dried and it is consolidated, by pressing and / or heating, to obtain a porous layer, preferably mesoporous and inorganic.
• said porous layer is deposited on said dense layer.
• said dense layer is deposited on said mesoporous layer.
• a second electrode layer is deposited on said porous layer.
• said second electrode layer is a dense electrode, deposited by a method according to the first aspect of the invention.
• said second electrode layer is a porous electrode, preferably prepared according to the process for preparing a porous separator layer in relation to this fourth aspect of the invention, and in particular according to its first, second, third, fourth, and fifth variant, the separator material being replaced by a suitable electrode material, and preferably using an anode material or a cathode material according to the seventh variant of the first aspect of the invention.
• said porous separator layer is impregnated with a liquid carrying mobile lithium ions, which is preferably selected from the group formed by: an electrolyte composed of at least one aprotic solvent and at least one salt of lithium; o an electrolyte composed of at least one ionic liquid or ionic polyliquid and at least one lithium salt; o a mixture of at least one aprotic solvent and at least one ionic liquid or ionic polyliquid and at least one lithium salt; o a polymer made ionic conductive by adding at least one lithium salt; and o a polymer rendered ionic conductive by the addition of a liquid electrolyte, either in the polymer phase or in the mesoporous structure, said polymer preferably being selected from the group formed by poly (ethylene oxide), poly ( propylene oxide), polydimethylsiloxane, polyacrylonitrile,
• a fifth aspect of the invention is a dense layer capable of being obtained by the method according to the first aspect of the invention, with all the variants and all the sub-variants stated in relation to this first aspect of the invention.
• said material P is selected so that said dense layer can function as an anode in a lithium ion battery.
• said material P is selected so that said dense layer can function as a cathode in a lithium ion battery.
• said material P is selected so that said dense layer can function as an electrolyte in a lithium ion battery.
• said dense layer has a density of at least 90% of the theoretical density, preferably at least 95% of the theoretical density, and even more preferably at least 96% of the theoretical density, and optimally at least 97% of the theoretical density.
• a sixth aspect of the invention is a dense layer in a lithium ion battery obtainable by the method according to the first aspect of the invention, with all the variants and all the sub-variants stated in relation to this first aspect of the invention.
• said material P is selected so that said dense layer can function as an anode in a lithium ion battery.
• said material P is selected so that said dense layer can function as a cathode in a lithium ion battery.
• said material P is selected so that said dense layer can function as an electrolyte in a lithium ion battery.
• a seventh aspect of the invention is a lithium ion battery with a capacity greater than 1 mA h, comprising at least one dense layer according to the fifth aspect of the invention, with all the variants and all the sub-variants set out in relationship with this fifth aspect of the invention.
• said battery comprises an anode which is a dense layer according to the fifth aspect of the invention.
• said battery comprises a cathode which is a dense layer according to the fifth aspect of the invention.
• said battery comprises an anode and a cathode which are dense layers according to the fifth aspect of the invention.
• said battery comprises an anode and a cathode and an electrolyte which are dense layers according to the fifth aspect of the invention.
• said battery comprises a separator which is a porous layer according to the fourth aspect of the invention.

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• 2021
  • 2021-03-30 WO PCT/IB2021/052606 patent/WO2021198892A1/fr not_active Ceased
  • 2021-03-30 IL IL296739A patent/IL296739A/en unknown
  • 2021-03-30 EP EP21714695.0A patent/EP4128387A1/fr not_active Withdrawn
  • 2021-03-30 US US17/907,444 patent/US20230131454A1/en not_active Abandoned
  • 2021-03-30 JP JP2022559904A patent/JP2023527955A/ja not_active Withdrawn
  • 2021-03-30 CA CA3173400A patent/CA3173400A1/fr active Pending
  • 2021-03-30 CN CN202180038677.2A patent/CN115943503A/zh active Pending
  • 2021-03-30 KR KR1020227037967A patent/KR20220161451A/ko not_active Withdrawn

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