Classifications

• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
  • H01M4/623—Binders being polymers fluorinated polymers
• • 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
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • 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
  • H01M4/0411—Methods of deposition of the material by extrusion
• • 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
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • 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
  • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • 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
  • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • 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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
  • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
• • 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
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • 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

Definitions

• the present invention relates to the field of energy storage, and more specifically to accumulators, in particular of the lithium type.
• lithium accumulators The operation of lithium accumulators is based on the reversible exchange of lithium ion between a positive electrode and a negative electrode, separated by a separator containing an electrolyte, the lithium inserting itself into the negative electrode during charging operation .
• the electrodes consist of a metal strip on which is applied an electrode formulation consisting of active material and possibly binder and conductive element.
• WO 2015/161289 describes an electrode composition based on polytetrafluoroethylene (PTFE) and co-binder(s), obtained by fibrillation of PTFE by a high shear process such as air jet grinding (jet -milling) in particular.
• PTFE polytetrafluoroethylene
• co-binder(s) obtained by fibrillation of PTFE by a high shear process such as air jet grinding (jet -milling) in particular.
• PTFE has the particularity when sheared well to produce fibrils which form a network which contributes to the formation of porosities within the electrode.
• the jet-milling step may require batch work, which is incompatible with continuous industrial operation. Furthermore, grinding by jet-milling can damage the fragile active material (such as graphite for example).
• the present invention thus relates to a new solvent-free route for the improved preparation of electrode formulations, in particular intended for Li-ion technology.
• the present invention relates to a method for preparing an electrode formulation comprising:
• fluoropolymer refers to fluorinated polymers whose repeating unit is a fluorocarbon, comprising multiple carbon-fluorine bonds.
• fluoropolymers mention may in particular be made of polytetrafluoroethylene (PTFE) and its derivatives, in particular its co-polymers such as chlorofluoroethylene, perfluoroalkoxy (PFA), polychlorotrifluoroethylene (PCTFE or PTFCE), fluorinated ethylene propylene (FEP), ethylene tetrafluoroethylene or poly(ethylene-co-tetrafluoroethylene) (ETFE), tetrafluoroethylene perfluoromethylvinylether (MFA), more particularly PTFE.
• PTFE polytetrafluoroethylene
• PFA perfluoroalkoxy
• PCTFE or PTFCE polychlorotrifluoroethylene
• FEP fluorinated ethylene propylene
• ETFE ethylene tetrafluoroethylene
• said fluoropolymers are of the fibrillable type.
• fibrillable means the types of fluoropolymers which are capable of fibrillating, that is to say which can form a network of fibers in the mixture with the pre-mix, under the extrusion conditions.
• the types of fluoropolymers can be of different shapes and/or grades.
• Pre-mix means a preliminary composition prepared beforehand before adding one or more additional ingredients; in this case the pre-mix comprises the mixture of the fluoropolymer and the active material, and optionally a conductive element, before subsequent addition of the co-binder.
• the pre-mix can also include one or more optional additives such as lubricants.
• the pre-mix can also comprise particles of solid electrolyte.
• the active electrode material can be chosen from electrochemically active materials. It depends on the type of electrode (positive or negative) and the type of battery considered. Thus in the case of lithium batteries, the negative electrode active material is in particular graphite, silicon, lithium, a lithium alloy or a lithiophilic material, alone or as a mixture, such as mixed active materials SiOx / graphite .
• the expression “lithiophile” here defines a material having an affinity for lithium, (ie) its ability to form alloys with lithium, such as silicon, silver, zinc and magnesium.
• TNO titanium and niobium oxide
• active materials - a titanium and niobium oxide TNO having the formula: LixTia-yMyNbb-zM'zO((x+4a+5b)/2)-c-dXc where 0 ⁇ x ⁇ 5 ; 0 ⁇ y ⁇ 1; 0 ⁇ z ⁇ 2; 1 ⁇ a ⁇ 5; 1 ⁇ b ⁇ 25; 0.25 ⁇ a/b ⁇ 2; 0 ⁇ c ⁇ 2 and 0 ⁇ d ⁇ 2; ay >0; bz >0; M and M' each represent at least one element selected from the group consisting of Li, Na, K, Mg, Ca, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Y, Zr, Nb, Mo, Ru, Ag, Sn, Sb, Ta, W, Bi, La, Pr, Eu, Nd and Sm; X represents
• the subscript d represents an oxygen vacancy.
• the index d may be less than or equal to 0.5.
• Said at least one titanium and niobium oxide can be chosen from TiNb2O7, Ti2Nb2O9 and Ti 2 Nb 10 O 29 . - a lithiated titanium oxide or a titanium oxide capable of being lithiated.
• LTO is chosen from the following oxides: Li xa M a Ti yb M' b O 4-cd X c in which 0 ⁇ x ⁇ 3;1 ⁇ y ⁇ 2.5;0 ⁇ a ⁇ 1;0 ⁇ b ⁇ 1; 0 ⁇ c ⁇ 2 and - 2.5 ⁇ d ⁇ 2.5; M represents at least one element selected from the group consisting of Na, K, Mg, Ca, B, Mn, Fe, Co, Cr, Ni, Al, Cu, Ag, Pr, Y and La; M' represents at least one element selected from the group consisting of B, Mo, Mn, Ce, Sn, Zr, Si, W, V, Ta, Sb, Nb, Ru, Ag, Fe, Co, Ni, Zn, Al , Cr, La, Pr, Bi, Sc, Eu, Sm, Gd, Ti, Ce, Y and Eu; X represents at least one element selected from the group consisting of S, F, Cl and Br; The subscript d represents an oxygen deficiency.
• the index d may be less than or equal to 0.5;
• HxTiyO4 in which 0 ⁇ x ⁇ 1; 0 ⁇ y ⁇ 2, and a mixture of the compounds Lix-aMaTiy-bM'bO4-c-dXc and HxTiyO4.
• lithium titanium oxides are spinel Li4Ti5O12, Li2TiO3, ramsdellite Li2Ti3O7, LiTi2O4, LixTi2O4, with 0 ⁇ x ⁇ 2 and Li2Na2Ti6O14.
• a preferred LTO compound has the formula Li4-aMaTi5-bM'bO4, for example Li4Ti5O12 which is also written Li4/3Ti5/3O4.
• the active material of the positive electrode is not particularly limited.
• M' and M" being different from each other, and 1 ⁇ x ⁇ 1.4; 0 ⁇ y ⁇ 0.6; 0 ⁇ z ⁇ 0.2; - a compound (c) of formula Li x Fe 1-y M y PO 4 (LFMP) where M is chosen from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo; and 0.8 ⁇ x ⁇ 1.2; 0 ⁇ y ⁇ 0.6; - a compound (d) of formula Li x Mn 1-yz M' y M'' z PO 4 (LMP), where M' and M'' are different from each other and are chosen from the group consisting of in B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, with 0.8 ⁇ x ⁇ 1.2; 0 ⁇ y ⁇ 0.6; 0.0 ⁇ z ⁇ 0.2; - a compound (e) of formula xLi 2 M
• M represents at least one element chosen from the group consisting of Na, K, Mg, Ca, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Y, Zr, Nb, Mo, Ru, Ag, Sn, Sb, Ta, W, Bi, La, Pr, Eu, Nd and Sm and where 0 ⁇ x ⁇ 0.5 and 0 ⁇ y ⁇ 1;
• a conductive element can also be added for positive electrode preparation. It can be chosen from electronically conductive materials, such as graphite, carbon black, acetylene black, soot, graphene, carbon fibers, carbon nanotubes or a mixture thereof.
• the preparation of the pre-mix can be carried out by simple mixing of the constituents, typically in the form of powders, with stirring.
• the mixing step can advantageously be carried out at a temperature between 25°C and the degradation temperature of the fluoropolymer
• co-binder means a material which makes it possible to give the electrode the cohesion of the various components and its mechanical strength on the current collector, and/or to give a certain flexibility to the electrode. electrode for its implementation in the cell. More particularly, the co-binder according to the invention ensures the cohesion between the fluoropolymer and the active material.
• the co-binder is chosen from thermoplastic polyurethane (TPU), poly(styrene-butadiene-styrene) (SBS), poly(styrene-ethylene-butadiene-styrene) (SEBS), elastomers thermoplastics (TPE), vulcanized thermoplastics (TPV), thermoplastic copolyesters (TPC), polystyrene-b-poly(ethylene-butylene)-b-polystyrene (SEBS), butadiene-acrylonitrile copolymers also called “nitrile rubbers” (NBR ), hydrogenated butadiene-acrylonitrile copolymers, also called “hydrogenated nitrile rubbers” (HNBR), elastomers, thermoplastics or ethylene-acrylate terpolymers.
• TPU thermoplastic polyurethane
• SBS poly(styrene-butadiene-styrene)
• SEBS poly(s
• the co-binder is TPU.
• extrusion is meant a thermomechanical process according to which the formulation is forced to pass through a die, under the action of pressure and heat.
• the extrusion step can be adapted according to several parameters, such as the mixing temperature, the type of screw profile of the extruder, the type of die of the extruder, the rotation speed and/or the screw length.
• the extrusion can be carried out with a mono- or twin-screw type extruder, co-rotating or not.
• the screw profile used in the extruder is of the shearing type in order to cause the fluoropolymer to fibrillate in the extruder.
• the screw profile can contain one or more mixing zones. The number of mixing zones typically depends on the number of introduction zones. The position of the mixing zones in the extruder generally depends on the number of material introduction zones. After each material introduction zone, a mixing zone can be added.
• the type of screw element used to shear the material can be adapted to the type of active material contained in the pre-mix. If the active ingredient is sensitive to shearing, it is preferable to favor low or medium shearing elements. If the active material is not very sensitive to shearing, it is possible to use low, medium or high shearing elements.
• the rotational speed of the screw is generally the same throughout the screw. It is generally recommended to run it between 100rpm and 1000rpm, especially between 100 and 750 rpm.
• the speed of rotation of the screw is generally adapted according to the flow of material desired at the exit of the extruder. The lower the rotational speed of the screw, the lower the output flow rates. Note that low rotation speeds lead to longer residence times in the extruder. In such a case, if the material input flow is high, there may be a risk of clogging the extruder. In the case of a high screw rotation speed, the output flow rates can be fluctuating if the incoming material flow rates are too low.
• the extrusion step can advantageously be carried out at a temperature between 25° C. and the degradation temperature of the fluoropolymer, more particularly between the melting temperature of the co-binder and the melting temperature of the fluoropolymer under the extrusion conditions.
• the degradation and/or melting temperatures of the fluoropolymer under the extrusion conditions may be reduced due to the mechanical stresses exerted.
• the degradation temperature is approximately 350°C and the melting temperature is approximately 327°C, it being understood that due to the stresses exerted, the extrusion temperature is preferably lower or equal to 260°C.
• the present invention also relates to the electrode formulation capable of being obtained by the process according to the invention.
• the present invention also relates to an electrode formulation comprising:
• thermoplastic polyurethane TPU
• the fluoropolymer is as defined above.
• the aforementioned electrode formulations according to the invention may also comprise a conductive element. This is notably the case for the positive electrodes, as discussed above.
• the electrode formulations according to the invention may also comprise one or more additives chosen from lubricants such as oils or waxes or graphite.
• formulations according to the invention can also comprise a carbon additive.
• This additive is distributed in the electrode so as to form an electronic percolating network between the active material and the current collector.
• the carbonaceous additive can be comprised up to about 10% (by weight), in particular from 1 to 6% (weight) of the total content of the formulation.
• formulations according to the invention comprise (by weight):
• the electrode formulation according to the invention is suitable for positive or negative electrodes.
• negative electrode designates when the accumulator is discharging, the electrode functioning as an anode and when the accumulator is charging, the electrode functioning as a cathode, the anode being defined as the electrode where a electrochemical oxidation reaction (emission of electrons), while the cathode is the seat of reduction.
• negative electrode also designates the electrode from which the electrons leave, and from which the cations (Li+) are released in discharge.
• positive electrode designates the electrode where the electrons enter, and where the cations (Li+) arrive in discharge.
• the electrode formulation is porous, the porosity being imparted by the fluoropolymer fibrils generated by the extrusion.
• This porosity makes it possible in particular on the one hand to accommodate the lithium metal in the porosity of the negative electrode during charging, and on the other hand to maintain the mechanical strength of the electrode.
• the term "porous" means a pore size of less than 300 nm.
• the pore size corresponds to the structure of the material having an organized network of channels of variable very small pore size: typically a pore size of less than 1 ⁇ m, preferably less than 300 nm. This pore size gives the electrode a particularly large active surface per unit electrode surface.
• the electrode has a porosity of between 10 and 60%, preferably between 15 and 35%, the porosity representing the percentage of voids in the total volume of the formulation considered. Porosity can be measured by Hg porosimetry or by Helium porosimetry in general.
• the present invention also relates to an electrode comprising the electrode formulation according to the invention shaped.
• said electrode may consist of a conductive support used as a current collector which is coated with the formulation according to the shaped invention.
• current collector is meant an element such as a pad, plate, sheet or other, made of conductive material, connected to the positive or negative electrode, and ensuring the conduction of the flow of electrons between the electrode and the terminals of the battery.
• the current collector is preferably a two-dimensional conductive support such as a solid or perforated strip, based on metal, for example copper, nickel, steel, stainless steel or aluminum.
• Said electrode can in particular be a Li-ion type electrode.
• the latter advantageously consists of the formulation comprising PTFE, TPU and graphite shaped on a current collector such as a copper strip .
• the latter advantageously consists of the formulation comprising PTFE, TPU, an active positive electrode material, an electronically conductive element and a carbonaceous additive, shaped on a current collector such as aluminum foil.
• the electrodes according to the invention can be prepared by applying or adapting conventional methodologies for manufacturing electrodes.
• the formulation obtained at the end of the extrusion step is shaped, for example by pressing, to obtain a self-supporting formulation which will then be rolled by calendering, for example on the current collector.
• the present invention also relates to an electrochemical element comprising at least one electrode according to the invention.
• Electrochemical element means an elementary electrochemical cell made up of the positive electrode/electrolyte/negative electrode assembly, allowing the electrical energy supplied by a chemical reaction to be stored and returned in the form of current.
• the chemical elements according to the invention can be adapted to the different battery technologies and types of electrolytes.
• the electrochemical element can be of the lithium-ion type.
• Li-ion cells are based on the reversible exchange of lithium ion between a positive electrode and a negative electrode, separated by an electrolyte, the lithium being deposited at the negative electrode during charging operation.
• the positive electrode formulation comprises a lithiated transition metal oxide as active material and the negative electrode formulation comprises graphite as active material.
• the electrochemical element can also be of the “solid” or even “primary Li” type.
• solid designates elements with a solid electrolyte, such as oxides, halides, sulphides or a polymer.
• Li-primary refers to a non-rechargeable lithium cell.
• the present invention also relates to an electrochemical module comprising the stacking of at least two elements according to the invention, each element being electrically connected with one or more other element(s).
• module therefore designates here the assembly of several electrochemical elements, said assemblies possibly being in series and/or parallel.
• Another object of the invention is also a battery comprising one or more modules according to the invention.
• battery or accumulator is meant the assembly of several modules according to the invention.
• the batteries according to the invention are accumulators whose capacity is greater than 100 mAh, typically 1 to 100 Ah.
• Figure 1 represents the observation by SEM of the structure of an anode of 94% Graphite / 2% PTFE / 4% TPU formulation prepared according to the examples.
• Figure 2 represents the comparison of the pore size distribution for a reference anode (represented by circles) and for anodes according to the invention (varying in terms of their PTFE or TPU content) ( samples 1 , 2 and 3 represented by squares, diamonds and triangles, respectively)
• Figure 3 represents the comparison of the amount of porosity for a reference anode (round) and for anodes according to the invention (varying by their PTFE or TPU content) (samples 1, 2 and 3 : squares, diamonds and triangles, respectively).
• Electrode formulations according to the invention are prepared by producing a premix of the active material (graphite) and the fibrillable PTFE. Then the pre-mix is mixed with the binder (TPU) using a twin-screw extruder, at a temperature between 70 and 260° C. and at a speed of rotation between 100 and 750 rpm.
• the mixture recovered at the exit of the extruder is then transferred to a mixer with external rollers to manufacture a self-supporting electrode (or pressed under a press) and to shape the electrode. Adhesion on strip is then obtained by co-lamination (by calendering) on a current collector.
• the SEM image in Figure 1 shows that the PTFE fibrils are well distributed in the electrode. They form a network which contributes to the formation of porosities within the electrode.
• the porosity was measured by porosimetry Fig.
• the reference electrode was produced by the solvent route.
• the active material (the graphite), the binder (the SBR) and the co-binder (the CMC) all in the form of powder, are first mixed in a dry process using a planetary-type mixer.
• a solvent NMP
• NMP solvent
• the formulation of the reference electrode is composed of 97% active material, 1.5% binder and 1.5% co-binder.
• the pre-mix/solvent mass ratio when adding the solvent is 40/60.
• the reference electrode is represented by circles, and the invention formulations 1, 2 and 3 above are represented by squares, diamonds and triangles, respectively.
• Figure 2 illustrates the size distribution of the pores contained in the reference electrode and in the electrodes made via the present invention. Two populations of pores are observed. It appears that the size distribution of the pores contained in the electrodes made by the process described in this invention is in the range of the size of the pores of the reference electrode prepared in the standard way (solvent way). In addition, Figure 2 shows that by changing the amount of PTFE and co-binder (here TPU) in the specific formulation, it is possible to control and modulate the amount of porosity produced but also the average pore size of the electrode.
• Figure 3 shows the amount of porosity contained in the reference electrode prepared by the solvent route and in electrodes prepared according to the method presented in the present invention.
• the amount of porosity of the electrodes prepared according to the method presented depends on the formulation. Moreover, it is shown that it is possible to modulate the amount of porosity of the electrode by adjusting the formulation, namely the content of active material, binder and co-binder.

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• 2021
  • 2021-06-16 FR FR2106383A patent/FR3124327B1/fr active Active
• 2022
  • 2022-06-15 WO PCT/EP2022/066388 patent/WO2022263555A2/fr not_active Ceased
  • 2022-06-15 EP EP22734280.5A patent/EP4356453A2/de active Pending
  • 2022-06-15 US US18/571,302 patent/US20240290981A1/en active Pending
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