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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/362—Composites
  • H01M4/364—Composites as mixtures
• • 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
• • 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
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/44—Methods for charging or discharging
• • 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
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/44—Methods for charging or discharging
  • H01M10/446—Initial charging measures
• • 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
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
• • 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
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
  • H01M10/488—Cells or batteries combined with indicating means for external visualization of the condition, e.g. by change of colour or of light density
• • 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
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • 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
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • 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
  • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• • 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
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • 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
  • H01M2004/028—Positive 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 technical field of the present invention is that of active materials intended to be used in the cathode of an electrochemical element of the lithium-ion type, also called lithium-ion element.
• the technical field is also that of methods for detecting the end of the charge of lithium-ion elements whose cathodic active material comprises a lithiated phosphate of at least one transition metal.
• Electrochemical elements of the lithium-ion type comprising a cathode whose active material is based on lithium phosphate of at least one transition metal are known from the state of the art.
• a lithiated phosphate of at least one transition metal typically has the formula UMPO4 where M represents at least one transition metal, for example Mn or Fe or Mn associated with Fe.
• Such elements have a mass capacity lower than that of elements whose cathode comprises an active material which is a lithiated oxide of at least one transition metal of formula UMO2 where M represents at least one transition metal.
• FIG. 1 An example of a charge profile of an element whose cathode comprises a li thie phosphate of at least one transition metal is shown in Figure 1.
• the present invention provides a mixture comprising:
• lithiated nickel oxide chosen from: i) a lithiated oxide of nickel, manganese and cobalt of formula Li w (Ni x Mn y Co z M t )0 2 where 0.9 ⁇ w ⁇ 1.1;0.80 ⁇ x;0 ⁇ y;0 ⁇ z;0 ⁇ t; M being at least one element selected from the group consisting of Al, B, Mg, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, W, Mo, Sr, Ce, Ta, Ga, Nd, Pr, La; ii) a lithium oxide of nickel, cobalt and aluminum of formula Li w (Ni x Co y Al z M t )0 2 where 0.9 ⁇ w ⁇ 1.1;0.83 ⁇ x;0 ⁇ y;0 ⁇ z;0 ⁇ t; M being at least one element selected from the group consisting of B, Mg, Si, Ca, Ti, V, Cr, Mn, Fe,
• the incorporation into the lithium phosphate of a nickel-rich lithium oxide made it possible to obtain a mixture of active materials which, when used in the cathode of a lithium-electrochemical element ion can be used to detect the imminence of the end of the charge of the element, thus avoiding a start of overcharging.
• the charge profile of the element presents an indicator plate of the end of the charge of the element. This plateau appears for a state of charge close to 90-95%. The appearance of the plateau results in a slowing down of the increase in tension. It can be detected by analyzing periodically or at predetermined times the variation in the voltage of the element over time. After detection of the tray, a signal indicating the imminence of the end of the charge can be sent to a user.
• said at least one lithiated nickel oxide is monocrystalline.
• said at least one lithiated nickel oxide is in the form of particles whose size distribution is characterized by a volume median diameter Dv 5 o less than or equal to 7 ⁇ m, preferably ranging from 2 to 6 ⁇ m, the median diameter being measured on particles which are not part of an agglomerate of particles.
• the mixture comprises:
• the mixture comprises:
• the index x of the nickel ranges from 0.84 to 0.90.
• the index x of the nickel is less than or equal to 0.98 or less than or equal to 0.90.
• the 1-y-z index of manganese ranges from 0.6 to less than 1.
• the invention also relates to an electrochemical element comprising:
• the subject of the invention is a method for detecting the end of the charge of a lithium-ion electrochemical element, said method comprising the steps of: a) providing an electrochemical element as described above, b) charge of the cell, c) for a state of charge of the cell greater than approximately 70%, or greater than approximately 80%, or greater than or equal to 85%, or greater than or equal to 90 %, calculation at periodic or predetermined instants of the value of the derivative of the voltage with respect to time dV/dt, d) sending of a signal indicating the imminence of the end of the charge if the value of the derivative dV/dt is below a predetermined threshold.
• FIG. 1 shows the charge profile of an element whose cathode comprises as electrochemically active material only a lithium phosphate of manganese and iron.
• FIG. 2 shows the load profiles of the elements prepared in the examples.
• FIG. 3 is a magnification of the load profiles shown in Figure 2.
• the addition to the lithiated phosphate of at least one nickel-rich lithiated oxide makes it possible to obtain a mixture whose charge profile presents a plateau as the end of the charge approaches. of the element.
• the term "rich in nickel” denotes in the following a stoichiometric nickel index greater than or equal to 0.80 for the lithiated oxide of nickel, manganese and cobalt and greater than or equal to 0.83 for the lithiated nickel oxide , cobalt and aluminum.
• the proportion of the lithiated oxide ranges from 1 to less than 50% of the mass of all the active materials present in the cathode. It can range from 5 to 40% or from 10 to 30% or from 15 to 25% of the mass of all the active materials present in the cathode.
• the lithiated nickel oxide is said to be lamellar because it consists of a stack of layers of formula MO2, where M designates one or more transition elements.
• M designates one or more transition elements.
• Each sheet is made up of the association of MOb octahedra sharing their edges.
• the center of each octahedron is occupied by a transition element M and the six vertices of the octahedron are occupied by an oxygen atom.
• the lithium atom is intercalated between the MO2 sheets. During the charging of the electrochemical cell, it disintercalates from the sheets. During the discharge of the element, it is reintercalated between the layers.
• the nickel of the lithiated oxide can be combined with manganese, cobalt, and optionally one or more chemical elements to give the compound of formula Li w (Ni x Mn y Co z M t )0 2 abbreviated NMC where 0.9 ⁇ w ⁇ 1.1;0.80 ⁇ x;0 ⁇ y;0 ⁇ z;0 ⁇ t; M being at least one element selected from the group consisting of Al, B, Mg, Si, Ca, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, W, Mo, Sr, Ce, Ta, Ga, Nd, Pr and La.
• Preferred NMC compounds 1)-3) satisfy the following criteria:
• x may be at least equal to 0.82 or at least equal to 0.84 or at least equal to 0.86 or at least equal to 0.88 or at least equal to 0.90.
• x can be at least equal to 0.86 or at least equal to 0.88 or at least equal to 0.90.
• x can be at least equal to 0.85 or at least equal to 0.86 or at least equal to 0.88 or at least equal to 0.90.
• NMC-like compounds are for example LiNio ,84 Mno , o 8 Coo , o 80 2 and Li N io,87Mno,o6Coo,o702, LiNio,89Mno,o6Coo,o502.
• Several NMC-like compounds may be present in the cathode.
• the nickel of the lithiated oxide can be combined with cobalt, aluminum and optionally one or more chemical elements to give the compound of formula Li w (Ni x CoyAl z M t )0 2 abbreviated N CA where 0.9 ⁇ w ⁇ 1.1;0.83 ⁇ x;0 ⁇ y;0 ⁇ z;0 ⁇ t; M being at least one element selected from the group consisting of B, Mg, Si, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Y, Zr, Nb, W, Mo, Sr, Ce, Ga, Ta, Nd, Pr and La.
• Preferred N CA compounds 1)-3) satisfy the following criteria:
• x can be at least equal to 0.84 or at least equal to 0.86 or at least equal to 0.88 or at least equal to 0.90 or at least equal to 0.92.
• x can be at least equal to 0.86 or at least equal to 0.88 or at least equal to 0.90.
• x can be at least equal to 0.85 or at least equal to 0.86 or at least equal to 0.88 or at least equal to 0.90.
• NCA type compounds rich in nickel are for example LiNio .84 Coo , osAlo , o 8 0 2 ,
• NCA-like compounds may be present in the cathode.
• a mixture of one or more NMC type compounds and one or more NCA type compounds can be used in the cathode.
• the lithiated nickel oxide can be a single crystal or a polycrystal.
• a monocrystal is a solid made up of a single crystal, formed from a single seed.
• a polycrystal is a solid made up of a set of crystals of varying size, shape and orientation, separated by grain boundaries.
• the lithiated nickel oxide is a single crystal. It has in fact been discovered that when the lithiated nickel oxide is in the form of a monocrystal, the electrochemical element has a better cycle life.
• a procedure given by way of indication for the manufacture of a monocrystal of the lithiated oxide of nickel, manganese and cobalt is as follows.
• aqueous solutions are prepared from a nickel salt, a manganese salt, a cobalt salt and a salt of the element M. Salts that are highly soluble in aqueous medium. It can for example be NÎS0 4 -6H 2 0, MnSO ôhhO, CoS0 4 -7H 2 0. The quantities of salts are calculated to correspond to the molar ratios Ni: Mn: Co: M of x: y: z: t.
• the aqueous solutions are simultaneously introduced into a continuously stirred reactor under a nitrogen atmosphere.
• a solution of NaOH for example 5 mol-L 1
• a solution of NH3 ⁇ 2O for example 4 mol-L 1
• chelating agent for example 4 mol-L 1
• the temperature for example 50°C
• the pH value for example 11.5
• the stirring speed of the solution for example 500 rpm
• Ni x Mn y Co z M t (OH)2 particles are obtained by washing, filtration and drying in a vacuum oven at 110° C. overnight. Then this precursor is mixed with LiOH-hhO.
• the molar quantity of lithium is in slight excess compared to the total molar quantity of the elements Ni, Mn, Co and M.
• the excess lithium is intended to compensate for the loss of lithium during the sintering process.
• the mixture is annealed at about 500°C for about 5 hours, then calcined at about 850°C for about 10 hours under an oxygen atmosphere to finally obtain the monocrystal of Li w Ni x Mn y Co z M t 0 2
• the preparation of a monocrystal of Li w Ni x Co y Al z M t 0 2 is carried out in a similar manner.
• the aluminum element is supplied in the form of an aqueous solution prepared from aluminum salts which are soluble in an aqueous medium. It can be sulphate or nitrate or aluminum chloride.
• the lithiated nickel oxide is used in the formulation of the cathode in the form of a powder of particles.
• the size distribution of the particles is characterized by a median volume diameter Dv 5 o less than or equal to 7 ⁇ m, or ranging from 2 to 6 ⁇ m, the median diameter being measured on particles not not part of an agglomerate of particles.
• the size distribution of the agglomerate of crystals is characterized by a median volume diameter Dv 5 o greater than or equal to 8 ⁇ m, ranging for example from 8 to 12 ⁇ m.
• the term "median diameter Dv 5 o equal to X pm" means that 50% of the volume of the lithiated nickel oxide particles is made up of particles having an equivalent diameter less than X pm, and 50% of the volume of the oxide particles Nickel lithium is made up of particles having an equivalent diameter greater than X pm.
• the term equivalent diameter of a particle designates the diameter of a sphere having the same volume as this particle. The measurement of the particle size can be carried out by the technique of granulometry by laser diffraction using a Malvern Mastersizer 2000 device.
• the lithium manganese iron phosphate has the formula Li x Mni- yz Fe y M z P0 4 (LMFP), where M is at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, with 0.8 ⁇ x ⁇ 1.2;0 ⁇ y ⁇ 0.5;0 ⁇ z ⁇ 0.2.
• LMFP Li x Mni- yz Fe y M z P0 4
• the stoichiometric index y of iron can be strictly less than 0.5 or less than or equal to 0.45 or less than or equal to 0.40 or less than or equal to 0.30 or less than or equal to 0.20. It may be greater than or equal to 0.05 or greater than or equal to 0.10 or greater than or equal to 0.20 or greater than or equal to 0.30 or greater than or equal to 0.40.
• Typical formulas for lithium manganese iron phosphate are LiMno.sFeo ⁇ PC, LiMno,7Feo,3P04, LiMn2/3Fe1/3P04 and LiMno,5Feo,5P04.
• the lithium manganese iron phosphate can be coated with a layer of a conductive material, such as carbon.
• the proportion of lithium phosphate ranges from more than 50% to 99%, or from 55 to 90% or from 60 to 80% or from 65 to 75% of the mass of all the materials active from the cathode.
• the presence of a majority of lithium phosphate gives the electrochemical element good thermal stability.
• a preferred mixture of active materials comprises:
• the cathode active material composition designates the set of compounds which cover the current collector of the cathode on at least one of its faces.
• this composition includes:
• electrochemically active materials that is to say said at least one lithiated nickel oxide, the lithiated manganese and iron phosphate described above and possibly one or more other electrochemically active materials;
• the function of the binder is to reinforce the cohesion between the particles of active material as well as to improve the adhesion of the mixture according to the invention to the current collector.
• the binder may be one or more of the following compounds: polyvinylidene fluoride (PVDF) and its copolymers such as polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polytetrafluoroethylene (PTFE) and its copolymers, polyacrylonitrile (PAN ), poly(methyl)- or (butyl)methacrylate, polyvinyl chloride (PVC), poly(vinyl formal), polyester, block polyetheramides, polymers of acrylic acid, methacrylic acid, acrylamide, itaconic acid, sulfonic acid, elastomers and cellulosic compounds.
• PVDF polyvinylidene fluoride
• PVDF-HFP polyvinylidene fluoride-co-hexaflu
• the elastomer or elastomers that can be used as binder can be chosen from styrene-butadiene (SBR), butadiene-acrylonitrile rubber (NBR), hydrogenated butadiene-acrylonitrile rubber (HNBR).
• SBR styrene-butadiene
• NBR butadiene-acrylonitrile rubber
• HNBR hydrogenated butadiene-acrylonitrile rubber
• the electronically conductive material is generally chosen from graphite, carbon black, acetylene black, soot, graphene, carbon nanotubes or a mixture thereof. It is used in small quantities, generally 5% or less relative to the sum of the masses of the mixture of active materials, of the binder(s) and of the electronically conductive material.
• An ink is prepared by mixing the cathode active materials, the binder(s), generally an electronically conductive material and at least one solvent.
• the solvent is an organic solvent which can be chosen from N-methyl-2-pyrrolidone (NMP), dimethyl formamide (DMF) and dimethyl sulphoxide (DMSO). It can also be chosen from cyclopentyl methyl ether (CPME), xylene (o-xylene, m-xylene or p-xylene), heptane, or a ketone-based solvent such as acetone or methyl ethyl ketone ( MEK).
• NMP N-methyl-2-pyrrolidone
• DMF dimethyl formamide
• DMSO dimethyl sulphoxide
• CPME cyclopentyl methyl ether
• xylene o-xylene, m-xylene or p-xylene
• heptane heptane
• MEK ketone
• the viscosity of the ink is adjusted by varying the quantity of solid materials, that is to say the cathodic active materials, the binder and the electronically conductive material, or else by varying the quantity of solvent.
• the ink is deposited on one or both sides of a current collector.
• This one is a current-conducting support, preferably two-dimensional, such as a solid or perforated strip, based on carbon or metal, for example nickel, steel, stainless steel or aluminum, preferably aluminum.
• the current collector can also be coated on one or both sides with a layer of carbon.
• the ink-coated current collector is placed in an oven and the solvent is evaporated.
• the quantity of solid material remaining after evaporation of the solvent can range from 35 to 65% or from 45 to 55% by mass relative to the mass of the ink before drying.
• the cathode can then be compressed during a calendering step. This step makes it possible to adjust the thickness of the layer of solid material deposited on the current collector.
• a typical composition of cathodic active material after drying is as follows:
• binder(s) from 1 to 10% by mass of binder(s), preferably from 1 to 5%;
• the anode is prepared in a conventional manner. It consists of a conductive support used as a current collector which is coated on one or both sides with a layer containing an anode active material and also generally a binder and an electronically conductive material.
• the current collector can be a two-dimensional conductive support such as a solid or perforated strip, in aluminum or in an aluminum-based alloy or in copper or in a copper-based alloy.
• the current collector can be coated on one or both sides with a layer of carbon.
• the anodic active material is not particularly limited. It is a material capable of inserting lithium into its structure. It can be chosen from lithium compounds, carbonaceous materials such as graphite, coke, carbon black and glassy carbon. It can also be based on tin, silicon, compounds based on carbon and silicon, compounds based on carbon and tin or compounds based on carbon, tin and silicon. It can also be a lithiated titanium oxide such as LÎ 4 Ti 5 0i 2 or a niobium titanium oxide such as TiNb2O7. It can also be made of lithium metal or of a lithium alloy with one or more chemical elements.
• the anode binder can be chosen from the following compounds, taken alone or as a mixture: polyvinylidene fluoride (PVDF) and its copolymers, polytetrafluoroethylene (PTFE) and its copolymers, polyacrylonitrile (PAN), poly(methyl)- or (butyl) methacrylate, polyvinyl chloride (PVC), poly(vinyl formal), a polyester, block polyetheramides, polymers of acrylic acid, methacrylic acid, a acrylamide, itaconic acid, sulfonic acid, elastomers and cellulosic compounds.
• PVDF polyvinylidene fluoride
• PTFE polytetrafluoroethylene
• PAN polyacrylonitrile
• PVC poly(methyl)- or (butyl) methacrylate
• PVC polyvinyl chloride
• PV formal poly(vinyl formal)
• block polyetheramides polymers of acrylic acid, methacrylic acid, a
• the electronically conductive material is generally chosen from graphite, carbon black, acetylene black, soot, graphene, carbon nanotubes or a mixture thereof. It is generally used at a rate of 7% or less relative to the sum of the masses of the mixture of anodic active material, of the binder and of the electronic conductive material.
• Lithium-ion element [0047] Lithium-ion element:
• the lithium-ion element is manufactured in a conventional manner. At least one cathode, at at least one separator and at least one anode are superposed. The assembly can be rolled to form a cylindrical electrochemical bundle.
• the invention is not limited to the manufacture of elements of cylindrical format.
• the format of the element can also be taken as matic or as a pouch type.
• the electrodes can also be stacked to form a planar electrochemical bundle.
• a connection part is fixed on an edge of the cathode not covered with active material. It is connected to a current output terminal.
• the anode can be electrically connected to the cell container. Conversely, the cathode can be connected to the cell container and the anode to a current output terminal.
• the electrochemical bundle After being inserted into the cell container, the electrochemical bundle is impregnated with electrolyte. The element is then closed tightly.
• the element can also be conventionally equipped with a safety valve causing the container of the element to open if the internal pressure of the element exceeds a predetermined value.
• the electrolyte can be liquid and comprise a lithium salt dissolved in an organic solvent.
• This lithium salt can be chosen from lithium perchlorate UCIO4, lithium hexafluorophosphate L1PF6, lithium tetrafluoroborate L1BF4, lithium hexafluoroarsenate LiAsF 6 , lithium hexafluoroantimonate LiSbF 6 , trifluoromethanesulfo- lithium ate UCF3SO3, lithium bis(fluorosulfonyl)imide Li(FS0 2 ) 2 N (LiFSI), lithium trifluoromethanesulfonimide LiN(CF 3 S0 2 ) 2 (LiTFSI), lithium trifluoromethanesulfone methide LiC( CF 3 S0 2 ) 3 (LiTFSM), lithium bisperfluoroethylsulfonimide LiN(C 2 F 5 S0 2 ) 2 (LiBETI), lithium 4,5-di
• the electrolyte solvent can be chosen from saturated cyclic carbonates, unsaturated cyclic carbonates, linear carbonates, alkyl esters, ethers, cyclic esters, such as lactones.
• the electrolyte can be solid. It may be a compound which conducts lithium ions, chosen for example from oxides which conduct lithium ions and sulphides which conduct lithium ions.
• the electrolyte can also be a polymer that conducts lithium ions, such as polyethylene oxide (PEO), polyphenylene sulfide (PPS) and polycarbonate.
• the electrolyte can also be in the form of a gel obtained by impregnating a polymer with a liquid mixture comprising at least one lithium salt and an organic solvent.
• the separator may consist of a layer of polypropylene (PP), polyethylene (PE), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), polyester such as polyethylene terephthalate (PET), poly( butylene) terephthalate (PBT), cellulose, polyimide, glass fibers or a mixture of layers of different types.
• PP polypropylene
• PE polyethylene
• PTFE polytetrafluoroethylene
• PAN polyacrylonitrile
• PET polyethylene terephthalate
• PBT poly( butylene) terephthalate
• cellulose polyimide
• glass fibers or a mixture of layers of different types.
• the polymers mentioned can be coated with a ceramic layer and/or polyvinylidene difluoride (PVdF) or poly(vinylidene fluoride-hexafluoropropylene (PVdF-HFP) or acrylates.
• PVdF polyvinylidene di
• FIG. 2 is an enlargement of FIG. 2 for states of charge close to the end of charging.
• the load profile of elements 3 and 4 has a plateau located between the flat part and the sudden rise in voltage.
• the plateau is visible for elements 3 and 4, whether it is monocrystalline NMC or polycrystalline NMC.
• the presence of this plateau can be detected using means for measuring the voltage of the element coupled to electronic means for processing the measured voltage values.
• the change in concavity of the load profile is detectable by computer means. The detection of the tray triggers a signal that warns a user of the imminence of the end of the charge.

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• 2021
  • 2021-04-22 FR FR2104226A patent/FR3122286B1/fr active Active
• 2022
  • 2022-04-08 WO PCT/EP2022/059488 patent/WO2022223327A1/fr active Application Filing
  • 2022-04-08 US US18/283,982 patent/US20240170645A1/en active Pending
  • 2022-04-08 CN CN202280027838.2A patent/CN117121227A/zh active Pending
  • 2022-04-08 EP EP22721392.3A patent/EP4327377A1/de active Pending

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