EP4128389A1 - Verfahren zur herstellung dichter schichten als elektroden und/oder elektrolyte für lithium-ionen-batterien und auf diese weise erhaltene lithium-ionen-mikrobatterien - Google Patents

Verfahren zur herstellung dichter schichten als elektroden und/oder elektrolyte für lithium-ionen-batterien und auf diese weise erhaltene lithium-ionen-mikrobatterien

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Publication number
EP4128389A1
EP4128389A1 EP21714977.2A EP21714977A EP4128389A1 EP 4128389 A1 EP4128389 A1 EP 4128389A1 EP 21714977 A EP21714977 A EP 21714977A EP 4128389 A1 EP4128389 A1 EP 4128389A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
layer
mixture
compounds
size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21714977.2A
Other languages
English (en)
French (fr)
Inventor
Fabien Gaben
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
I Ten SA
Original Assignee
I Ten SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by I Ten SA filed Critical I Ten SA
Publication of EP4128389A1 publication Critical patent/EP4128389A1/de
Pending legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
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    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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Definitions

  • the present invention relates to the manufacture of dense layers, usable in electrochemical devices, in particular as a layer of electrodes or electrolytes. These layers can be used in particular in multi-layer batteries, such as lithium ion microbatteries. They are made from inorganic nanoparticles, which may optionally have received functionalization with an organic coating layer, which may be polymeric. The invention also relates to a new process for manufacturing these dense layers from nanoparticles.
  • the invention also relates to the layers obtained by this process, and the multilayer microbatteries incorporating at least one layer obtained by this process.
  • 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.
  • STATE OF THE ART Lithium ion batteries have the best energy density among the various electrochemical technologies for storing electrical energy offered. There are different architectures and chemical compositions of electrodes for making lithium ion batteries. 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.
  • microbatteries i.e. rechargeable batteries of very small size, capable of being integrated on electronic cards; these electronic circuits can be used in many fields, for example in cards to secure transactions, in electronic labels, in implantable medical devices, in various micromechanical systems.
  • 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 '), casting in tape (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 of powders, the average particle size of which is 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. These techniques make it possible to produce layers with a thickness of between about 50 ⁇ m and about 400 ⁇ m. Depending on the thickness of the layers, their porosity and the size of the active particles, the power and energy of the battery can be modulated. To make microbatteries we would like to have a lower thickness.
  • 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 about 60% of the volume of the deposit, which means that there is generally 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 (an 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.
  • an electrolyte which can be liquid (an 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.
  • electrolyte can be liquid (an 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.
  • this electrolyte is liquid or gelled.
  • the slow diffusion within the electrode particles contributes to the series resistance of the battery.
  • the particle size must be reduced; in standard lithium ion batteries it is typically between 5 ⁇ m and 15 ⁇ m.
  • the size and density of the 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.
  • High power battery cells must use thin, high porosity electrodes and separators, while increasing energy density requires increasing these same thicknesses and reducing the porosity rate.
  • the ionic resistance increases sharply because some porosities are then liable to close, which prevents wetting of the electrode by the electrolyte. Consequently, when it is sought to produce electrode films without porosities in order to increase the energy density, it 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 is to deposit 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 therefore having excellent energy densities, and good temperature resistance.
  • PVD Physical Vapor Deposition
  • PVD deposition techniques make it possible to obtain films of very good quality, containing hardly any point defects, and allow deposition to be carried out 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 vacuum deposition techniques used to produce such films are very expensive and difficult to implement industrially on large surfaces, with high productivity.
  • the other technologies currently available for making dense ceramic films include embodiments based on the densification of compact deposits of particles or else the production of film by sol-gel type techniques.
  • 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 on 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. To increase the thickness of the deposit without inducing the risk of the appearance of cracks or cracks, it is necessary to proceed in successive stages.
  • the present invention seeks to remedy at least in part the drawbacks of the prior art mentioned above. More precisely, 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 microbatteries, 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 microbattery, a capacitor, a supercapacitor, a photovoltaic cell comprising a dense electrode or a dense electrolyte according to the invention. .
  • a method of manufacturing a dense layer comprising the steps of: supplying a substrate and a suspension of non-agglomerated nanoparticles of a material P, - deposition of 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 D 50 .
  • 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 than or equal to 50 nm; either - discontinuously: in this case the size distribution of the nanoparticles of material P comprises nanoparticles of a first size D1 between 50 nm and 20 nm, and nanoparticles of 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. 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 capable of being obtained by the method according to the first object. It can in particular be chosen from an anode, a cathode and / or an electrolyte for a lithium ion battery.
  • a third object of the invention is a dense layer in an electrochemical, electronic, electrical or electrotechnical device, such as a battery (and preferably a lithium ion battery), a capacitor, a supercapacitor, a capacitor, a resistor. , an inductor, a transistor, said dense layer being capable of being 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 fourth object of the invention is a method of manufacturing a dense layer in a lithium ion battery, said method having the characteristics of the method of manufacturing a dense layer stated above, all of the embodiments of which can be used for the production of a dense layer in a lithium ion battery.
  • a final object of the invention is an electrochemical device, and in particular a microbattery, and in particular a lithium ion microbattery, comprising at least one dense layer according to the second object of the invention.
  • said lithium ion microbattery comprises an anode and a cathode which are dense layers according to the invention. This anode and / or this cathode may have a thickness of between approximately 1 ⁇ m and approximately 50 ⁇ m.
  • its electrolyte layer can also be a dense layer according to the invention.
  • said microbattery comprises a liquid electrolyte infiltrated into a porous separator which separates said anode and said cathode.
  • This electrolyte layer or this separator advantageously has a thickness of between approximately 1 ⁇ m and approximately 20 ⁇ m, and preferably between approximately 3 ⁇ m and approximately 10 ⁇ m.
  • it is only its electrolyte layer which is a dense layer according to the invention.
  • the size of a particle is defined by its largest dimension.
  • 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 refer to 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 as a relative value (for example in percent), which is obtained by comparing the actual density of the layer (here referred to as d lying down ) and the theoretical density of the solid material which constitutes it (designated here as theoretical).
  • an electronically insulating material or layer preferably an electronically insulating and ionically conductive layer is a material or a layer whose electrical resistivity (resistance to the passage of electrons) is greater than 10 5 ⁇ cm.
  • ionic liquid any liquid salt, capable of transporting electricity, which differs from all molten salts by a melting point of less than 100 ° C. Some of these salts remain liquid at room temperature and do not solidify, even at very low temperatures. Such salts are called “ionic liquids at room temperature”.
  • the term “mesoporous” materials is understood to mean any solid which has within its structure so-called “mesopore” pores having a size intermediate between that of the micropores (width less than 2 nm) and that of the macropores (width greater than 50 nm). nm), namely a size between 2 nm and 50 nm.
  • nanopore is therefore not used here, even if the mesopores as defined above have nanometric dimensions within the meaning of the definition of nanoparticles, knowing the pores of size smaller than that of the mesopores are called by the those skilled in the art of "micropores".
  • a presentation of the concepts of porosity (and of the terminology which has just been exposed above) is given in the article “Texture of pulverulent or porous materials” by F.
  • the term “mesoporous layer” is understood to mean a layer which has mesopores. As will be explained below, in these layers, the mesopores contribute significantly to the total pore volume; this fact is reflected by the expression “Mesoporous layer of mesoporous porosity greater than X% by volume” used in the description below where X% is preferably greater than 25%, preferably greater than 30% and even more preferably between 30 and 50% of the total volume of the layer.
  • aggregate means, as defined by IUPAC, a loosely bound assembly of primary particles.
  • these primary particles are nanoparticles with a diameter that can be determined by transmission electron microscopy.
  • An aggregate of aggregated primary nanoparticles can normally be destroyed (i.e. reduced to primary nanoparticles) in suspension in a liquid phase under the effect of ultrasound, according to a technique known to those skilled in the art.
  • agglomerate means, as defined by IUPAC, a tightly bonded assembly of primary particles or aggregates.
  • electrochemical layer refers to the layer within an electrochemical device, this device being capable of operating according to its destination.
  • the electrolyte layer is an ionic conductor, but it is electronically insulating.
  • electrochemical device is a secondary lithium ion battery
  • electrochemical device layer designates either the dense electrolyte layer within which lithium cations move, or a “porous inorganic layer” impregnated with a phase carrying lithium ions.
  • Said porous inorganic layer in an electrochemical device is also referred to here as a "separator", according to the terminology used by those skilled in the art. 2.
  • the problem is solved by a method of 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 deposition of nanoparticles before sintering.
  • Obtaining the most compact deposit possible before sintering will reduce shrinkage and the risk of cracking.
  • it is not only necessary to perfectly control the size distribution of the nanoparticles but also to have the most compact possible deposit of these nanoparticles, without agglomeration.
  • 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 carried out 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), the size of the particles and 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. Once these organic compounds are removed, the nanoparticles will come into contact and begin the consolidation process.
  • colloidal suspensions of nanoparticles are used, the average 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 on the mean radius of the nanoparticles must be greater than 0.6. To increase this compactness of the initial deposit before sintering, it is also possible to use a mixture of two populations in nanoparticle sizes. In this case, 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 a sigma / R ratio.
  • 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 the largest nanoparticles, the size distribution of this second population could be narrower and potentially with a sigma / R ratio. avg less than 0.6.
  • 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.
  • the two populations should not show agglomeration in the ink produced.
  • these nanoparticles can be advantageously synthesized in the presence of ligands or organic stabilizers so as to avoid aggregation, or even agglomeration, of the nanoparticles.
  • the preparation of colloidal suspensions by wet nano-grinding allows fairly broad size distributions to be obtained. However, depending on the nature of the material crushed, from its "fragility" of the reduction rate applied, the primary nanoparticles can be damaged or amorphous.
  • 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.
  • These methods of synthesizing nanoparticles by precipitation make it possible to obtain primary nanoparticles of homogeneous size with a reduced size distribution, of good crystallinity and purity. It is also possible to obtain with these methods very small particle sizes, which may be less than 10 nm, and in a non-aggregated state.
  • 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, a printing process preferably chosen from inkjet printing (called “ink-jet” in English) and flexographic printing, and a coating process preferably chosen from among scraping (called “doctor blade” in English), roller coating (called “roll coating” in English), curtain coating (called “curtain coating” in English).
  • 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 metal foil. It must be selected so as to withstand the temperature of any thermal or thermomechanical treatment that 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).
  • a layer of conductive material of ITO type which has the advantage of also acting as a diffusion barrier.
  • a layer of conductive material of ITO type which has the advantage of also acting as a diffusion barrier.
  • ITO type which has the advantage of also acting as a diffusion barrier.
  • 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.
  • a dense ceramic deposit of Li 4 Ti 5 O 12 we can make an ink composed of nanoparticles of two different sizes, in the case of a Li anode 4 Ti 5 O 12 , we synthesize Li nanoparticles 4 Ti 5 O 12 glycothermally about 5 nm in diameter (see the article "Impact of the Synthesis Parameters on the microstructure of nano-structured LTO prepared by glycothermal routes and 7 Li NMR structural investigations ”, M. Odziomek, F.
  • Ligands are added to this synthesis in order to limit the agglomeration of the nanoparticles.
  • These 5 nm diameter nanoparticles are associated with Li nanoparticles 4 Ti 5 0 12 obtained by hydrothermal synthesis with particle sizes of 30 nm.
  • These 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 soaking deposition followed by the step of drying the layer can be repeated 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.
  • Treatment and properties of the deposited layers In general, 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 is raised 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 herein under the term "inorganic particles”.
  • 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 To Sn b O y NOT 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 NOT 1.72 ; as well as oxynitride-carbides of typical formula Si To Sn b VS vs O y NOT z with a> 0, b> 0, a + b ⁇ 2, 0 ⁇ c ⁇ 10, 0 ⁇ y ⁇ 24, 0 ⁇ z ⁇ 17; - Si-type nitri
  • - SnO oxides 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 , - TiNb composite oxides 2 O 7 comprising between 0% and 10% by mass of carbon, preferably the carbon being chosen from graphene and carbon nanotubes, - compounds of general formula Li w Ti 1-x M 1 xNb 2-y M 2 yO 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 may be the same or different from each
  • the layer according to the invention is to function as an electrolyte in a battery, especially 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 TO 1 xA 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 in the center of a tetrahedron formed by oxygen atoms, and d in which year TO 4 advantageously represents the silicate or zirconate anion, knowing that all or part of the elements T of an oxidation degree + IV can be replaced by atoms of an oxidation degree + III or + V, such
  • the nanoparticles used in the inks used to make these deposits intended for the electrodes can also have a core-shell structure. (better known under the English term “core - shell”).
  • core - shell the performance of the dense electrodes obtained by the process according to the invention 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 pass lithium ions, or by a graphite layer thin enough to pass lithium ions, or by an inorganic or organic layer of an ionic conductor which is also a good electronic conductor.
  • the core-bark approach can also be applied to the manufacture of electrolyte.
  • the core of the nanoparticles used in the method according to the invention is formed from an electrolyte material
  • 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.
  • the bark layer is an organic layer
  • this layer is made of a polymer material.
  • One advantage of a polymer layer is that it is 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 onto the surface of the nanoparticles a molecule exhibiting a structure of the Q- Z type in which Q is a function ensuring the attachment of the molecule to the surface.
  • the surface, and Z is preferably a PEO group.
  • group Q 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 in 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. More preferably, the nanoparticles inorganics are functionalized by 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 electrolyte nanoparticles or of electronic insulator so as to obtain a molar ratio between Q (which here comprises Q ') and all the cations present in the inorganic nanoparticles (here abbreviated "NP-C") of between 1 and 0.01, preferably between 0.1 and 0.02.
  • NP-C inorganic nanoparticles
  • the Q-Z molecule risks not being in sufficient quantity to ensure sufficient conductivity of the lithium ions; it also depends on the particle size. Using more Q-Z during functionalization would result in unnecessary consumption of Q-Z.
  • 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. At high concentrations, there may be a risk of bridging and a lack of accessibility of the surface to be functionalized (risk of precipitation of non-functional or poorly functionalized particles).
  • 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 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.
  • 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 material of solid electrolyte, preferably more than 60% and even more preferably more than 70% of solid electrolyte material.
  • 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 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.
  • 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 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 solid electrolyte particles.
  • the 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, 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 allows the deposition of dense inorganic layers in electrochemical and other devices, such as lithium ion batteries.
  • said dense layers can perform the function of an anode or a cathode or an electrode, and the device can include several dense inorganic layers according to the invention.
  • These devices can be of the "all solid" type, the dense layers exhibiting only very low porosity.
  • the device 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 D 50 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 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 lithium ion carrier phase 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 the addition of 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.
  • Example of manufacturing a lithium ion microbattery A method of manufacturing lithium ion microbatteries using the layers according to the invention is described here. a) Preparation of the electrodes by the deposition process according to the invention A first dense Li electrode was deposited 4 Ti 5 O 12 obtained by the process described above in the chapter "Deposition of a dense electrode layer by dip-coating”. A second dense LiMn electrode was also deposited 2 O 4 by a similar process. On each of these two electrodes, a thin mesoporous film of Li agglomerates was then deposited 3 PO 4 , which acts as a separator film in the battery, and which has been prepared as described below.
  • the solution obtained was added to 4.8 liters of acetone under the action of a homogenizer of Ultraturrax TM type in order to homogenize the medium. A white precipitation suspended in the liquid phase was immediately observed.
  • 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 was added to resuspend the precipitate (use of a sonotrode, magnetic stirring). Two more such washes were then performed with ethanol.
  • Agglomerates of around 200 nm made up of primary Li particles 3 PO 4 of 10 nm were thus obtained in suspension in ethanol.
  • Thin porous layers of Li 3 PO 4 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 nanoparticles 3 PO 4 previously obtained, for 90 seconds to obtain a layer of approximately 2 ⁇ m.
  • the layer was then air dried 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 stack was then thermo-compressed under a pressure of 45 MPa for 20 minutes, then the system was cooled to room temperature. Then the assembly was dried at 120 ° C for 48 hours under vacuum (10 mbar).
  • 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 (trifluoro- methanesulfonyl) imide.
  • LITFSI is the common abbreviation for lithium bis-trifluoromethanesulfonimide (CAS #: 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 lithium ion microbattery. In particular, it can be designed and dimensioned so as to have a capacity less than or equal to approximately 1 mA h (commonly called a “microbattery”).
  • microbatteries are designed to be compatible with microelectronics manufacturing processes. These micro-batteries can be produced: - either only with layers according to the invention, of the “all solid” type, ie devoid of impregnated liquid or pasty phases (said liquid or pasty phases possibly being a conductive medium of lithium ions.
  • a first aspect of the invention is a method of manufacturing a dense layer, which comprises the steps of: - Supplying a substrate and a suspension of non-agglomerated nanoparticles of an inorganic material P. - Deposit of a layer, on said substrate, from the suspension of primary nanoparticles of a P material. - Drying of the layer thus obtained. - Densification of the dried layer by mechanical compression and / or heat treatment.
  • 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 D 50 , such that: the distribution comprises nanoparticles of material P of a first size D1 between 20 nm and 50 nm, and nanoparticles of material P of a second size D2 characterized by a value D 50 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 D value 50 at least five times less 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.
  • 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 ratio avg 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 that of the first population of nanoparticles, and preferably at least one-twelfth.
  • this second population has a size distribution characterized by a sigma / R ratio avg 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.
  • said suspension has a viscosity, measured at 20 ° C., between 20 cP and 2000 cP.
  • 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, said method of manufacturing said dense layer being that according to the first aspect of the invention, with all the variants.
  • 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, said dense layer being 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.
  • a fourth aspect of the invention is a method of manufacturing a lithium ion battery, 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. '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, of mean primary diameter D 50 between 2 nm and 100 nm, preferably between 2 nm and 60 nm, said aggregates or agglomerates typically exhibiting an average diameter D 50 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.
  • 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 the addition of 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, polyacrylonit
  • a fifth aspect of the invention is a dense layer obtainable by the method according to the first aspect of the invention, with all the variants and all the sub-variants set out 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.
  • a seventh aspect of the invention is a lithium ion battery with a capacity not exceeding 1 mA h, referred to herein as a "microbattery", comprising at least one dense layer according to the fifth aspect of the invention, with all the variants and all the sub-variants stated in relation to this fifth aspect of the invention.
  • said microbattery comprises an anode which is a dense layer according to the fifth aspect of the invention.
  • said microbattery comprises a cathode which is a dense layer according to the fifth aspect of the invention.
  • said microbattery comprises an anode and a cathode which are dense layers according to the fifth aspect of the invention.
  • said microbattery comprises an anode and a cathode and an electrolyte which are dense layers according to the fifth aspect of the invention.
  • said microbattery comprises a separator which is a porous layer according to the fourth aspect of the invention.

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EP21714977.2A 2020-03-30 2021-03-30 Verfahren zur herstellung dichter schichten als elektroden und/oder elektrolyte für lithium-ionen-batterien und auf diese weise erhaltene lithium-ionen-mikrobatterien Pending EP4128389A1 (de)

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FR2003104A FR3108791A1 (fr) 2020-03-30 2020-03-30 Procede de fabrication de couches inorganiques denses, utilisables comme electrodes et/ou electrolytes pour microbatteries li-ion, et couches inorganiques denses ainsi obtenues
PCT/IB2021/052604 WO2021198890A1 (fr) 2020-03-30 2021-03-30 Procede de fabrication de couches denses, utilisables comme electrodes et/ou electrolytes pour batteries a ions de lithium, et microbatteries a ions de lithium ainsi obtenues

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WO2002003430A2 (en) * 2000-06-29 2002-01-10 California Institute Of Technology Aerosol process for fabricating discontinuous floating gate microelectronic devices
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DE10320936B4 (de) * 2003-05-09 2007-01-18 C. Hafner Gmbh + Co. Verfahren zur Herstellung keramischer Formkörper
FR2982082B1 (fr) * 2011-11-02 2013-11-22 Fabien Gaben Procede de fabrication de batteries en couches minces entierement solides
FR2982084B1 (fr) 2011-11-02 2013-11-22 Fabien Gaben Procede de fabrication d'electrodes de batteries entierement solides
FR2981952B1 (fr) 2011-11-02 2015-01-02 Fabien Gaben Procede de realisation de couches minces denses par electrophorese
FR2982086B1 (fr) 2011-11-02 2013-11-22 Fabien Gaben Procede de fabrication de micro-batteries en couches minces a ions de lithium, et micro-batteries obtenues par ce procede
FR2982083B1 (fr) * 2011-11-02 2014-06-27 Fabien Gaben Procede de realisation de films minces d'electrolyte solide pour les batteries a ions de lithium
US8993159B2 (en) * 2012-12-13 2015-03-31 24M Technologies, Inc. Semi-solid electrodes having high rate capability
FR3023302B1 (fr) * 2014-07-01 2016-07-15 I-Ten Batterie entierement solide comprenant un electrolyte solide a base de phosphate lithie, stable au contact de l'anode
US10411310B2 (en) * 2015-06-19 2019-09-10 24M Technologies, Inc. Methods for electrochemical cell remediation

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CA3173248A1 (fr) 2021-10-07
JP2023519703A (ja) 2023-05-12
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US20230148309A1 (en) 2023-05-11

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