EP4413630A2 - Verfahren zum betrieb einer lithiumbatterie - Google Patents

Verfahren zum betrieb einer lithiumbatterie

Info

Publication number
EP4413630A2
EP4413630A2 EP22801726.5A EP22801726A EP4413630A2 EP 4413630 A2 EP4413630 A2 EP 4413630A2 EP 22801726 A EP22801726 A EP 22801726A EP 4413630 A2 EP4413630 A2 EP 4413630A2
Authority
EP
European Patent Office
Prior art keywords
lithium
temperature
solid
charging
positive electrode
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
EP22801726.5A
Other languages
English (en)
French (fr)
Inventor
Marc Deschamps
Vincent BODENEZ
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.)
Blue Solutions SA
Original Assignee
Blue Solutions 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 Blue Solutions SA filed Critical Blue Solutions SA
Publication of EP4413630A2 publication Critical patent/EP4413630A2/de
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/443—Methods for charging or discharging in response to temperature
    • 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
    • H01M10/05—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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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 lithium batteries, more specifically to the field of lithium batteries with solid or quasi-solid electrolyte and in particular to the field of Lithium-Metal-Polymer (LMP) batteries in particular used for the production of electric vehicles and /or the storage of intermittent solar and/or wind energy.
  • LMP Lithium-Metal-Polymer
  • the invention relates more specifically to a method of operating a lithium battery in which the charging and discharging temperatures are modulated so as to obtain a battery with improved performance in terms of cycling resistance.
  • the Lithium Metal Polymer batteries currently on the market are “all-solid” batteries generally in the form of a thin film wound several times or several stacked thin films. This rolled up or stacked thin film has a thickness of the order of a hundred micrometers. It generally comprises at least four functional films: a negative electrode (anode) ensuring the supply of lithium ions during the discharge; a positive electrode (cathode) acting as a receptacle where the lithium ions are inserted; a solid polymer electrolyte conducting lithium ions and located between the positive electrode and the negative electrode; and a current collector connected to the positive electrode to provide electrical connection.
  • a negative electrode anode
  • a positive electrode cathode acting as a receptacle where the lithium ions are inserted
  • a solid polymer electrolyte conducting lithium ions and located between the positive electrode and the negative electrode and a current collector connected to the positive electrode to provide electrical connection.
  • the negative electrode is generally made of a sheet of metallic lithium or a lithium alloy
  • the solid polymer electrolyte is generally composed of a polymer based on poly(ethylene oxide) (POE) and at least one lithium salt
  • the positive electrode comprises an electrode active material, usually based on metal oxide (such as for example V2O5, U 3O8, LiCoOz, LiNiO2, LiMn2 ⁇ 4 or LiNio.5Mno.5O2) or based on UMPO4 type phosphate where M represents a metal cation selected from the group Fe, Mn, Co, Ni and Ti, and one of their combinations, and optionally carbon
  • the current collector is generally made of a sheet of metal.
  • the solid polymer electrolyte brings a great advantage in terms of safety since it avoids the use of potentially dangerous solvents in case of overheating. Such batteries can thus work at high temperatures without risk of explosion.
  • generally used solid polymer electrolytes such as high molecular weight POE doped with lithium salt, have low ionic conductivity at room temperature, so their operating temperature must be kept relatively high (typically between 70 and 100°C) .
  • the POE becomes a viscous liquid and loses its dimensional stability.
  • the main lines of research therefore aim to modify the solid polymer electrolyte to obtain improved mechanical properties and ionic conductivities maintained at lower temperatures.
  • Porcarelli et al. (Electrochimica Acta, 2017, 241, 526-534) describes polymer electrolytes of the polyurethane type obtained according to a process of polycondensation in several stages from isophorone diisocyanate, polyethylene glycol, and an anionic diol functionalized with a function ester and an imide anion of sulfonyl(trifluoromethylsulfonyl).
  • the latter is then functionalized with a crosslinkable function of the methacrylate type and then crosslinked by UV irradiation to form a film which is then impregnated with propylene carbonate to form an electrolyte.
  • gelled polymer (quasi-solid electrolyte).
  • the resistance to cycling of the gelled polymer electrolyte obtained is not entirely satisfactory insofar as a drop in capacity is observed beyond 10 cycles.
  • the object of the present invention is to overcome the drawbacks of the aforementioned prior art and to provide a lithium battery, and in particular a Lithium-Metal-Polymer (LMP) battery having good cycling stability (ie capable of operate over a large number of cycles). Indeed, the growing development of electric vehicles requires the availability of increasingly efficient batteries, in terms of cyclability.
  • the object of the invention is achieved by the method of operating a lithium battery which will be described below.
  • the inventors of the present application have in fact discovered, surprisingly, that it is possible to differentiate the charging temperature and the discharging temperature during the operation of a lithium battery in order to improve its resistance to cycling (also referred to as ci -after cyclability), while guaranteeing the use of a solid or quasi-solid electrolyte with good ionic conduction and mechanical properties.
  • the present invention thus has as its first object a method of operating a lithium battery chosen from lithium batteries with solid or quasi-solid electrolyte, said lithium battery comprising at least one positive electrode, at least one solid or quasi-solid electrolyte , and at least one negative electrode, said method being characterized in that it comprises at least the following steps: i) a step of charging the lithium battery at a charging temperature Te (in °C), and ii) a step of discharging the lithium battery at a discharging temperature TD (in °C), characterized in that the charging temperature Te (in °C) is strictly greater than the discharging temperature TD (in °C).
  • the charging temperature Tc (respectively the discharging temperature TD) is measured with a thermocouple of an oven, in particular sold under the trade name UNE500 by the company MEMMERT.
  • the charging temperature Te (respectively the discharging temperature TD) represents the temperature applied during operation of the battery during charging (respectively during discharging).
  • the lithium removed from the negative electrode in Li + ionic form migrates through the solid or quasi-solid electrolyte (eg ion-conductive polymer) and is inserted into the active material of the positive electrode.
  • the passage of each Li + ion in the internal circuit of the battery is exactly compensated by the passage of an electron in the external circuit, thus generating an electric current.
  • Steps i) and ii) of the method of the invention represent a charge-discharge process, also called cycling of the lithium battery.
  • the difference between the charging temperature Te during step i) and the discharging temperature TD during step ii) is at least approximately 5°C , particularly preferably at least about 7°C, and more particularly preferably at least about 10°C. Below a difference of 5°C, the resistance to cycling is not sufficient.
  • the difference between the charging temperature Te during step i) and the discharging temperature TD during step ii) is at most 50 approximately °C, particularly preferably at most approximately 40°C, more particularly preferably at most approximately 30°C, and even more particularly preferably at most approximately 20°C. Above a difference of 50°C, the method becomes more difficult to implement (heating of the battery during charging and cooling during discharging).
  • the difference between the charging temperature Te during step i) and the discharging temperature TD during step ii) (ie Te - TD) ranges from 20 to 35°, and more particularly preferably from 25 to 30°C approximately.
  • the charging temperature Te during step i) ranges from 0° C. to 100° C. approximately, preferably from 10° C. to 95° C. approximately, and in a particularly preferred manner from 20°C to 90°C approximately.
  • the discharge temperature TD during step ii) can range from -10° C. to 90° C. approximately, preferably from 0° C. to 85° C. approximately, and in a particularly preferred manner from 10° C. to 80° C. approximately.
  • the charging temperatures Te and discharging temperatures TD can be within ranges of equivalent values, with the condition that the charging temperature Te is strictly greater than the discharging temperature TD.
  • the method of operating a lithium battery in accordance with the invention can be applied to any type of lithium battery chosen from LMP batteries, and this regardless of the nature of the active material entering into the composition of the positive electrode. and/or whatever the nature of the solid or quasi-solid electrolyte.
  • the “solid or quasi-solid” electrolyte is in a solid form or in a gel form, at room temperature (i.e. 18-25° C.) and preferably in a solid form.
  • the reduction in the operating temperature of the battery between the charging step i) and the discharging step ii) has no influence on the charging potential Uc during the charging stage i) and the discharge potential UD during the discharging stage ii) (i.e. no variation in potential from Uc to UD linked to the variation in temperature from Te to TD is observed).
  • Step i) can be performed by heating the battery to the charging temperature Te and maintaining this temperature Te, preferably until a state of charge of approximately 95% is obtained.
  • the temperature Te is preferably constant during step i).
  • the heating of step i) can be carried out using at least one of the following heating means: use of hot forced air, use of a liquid heating circuit, or one or more plates heating, and preferably use of one or more heating plates.
  • Step ii) can be performed by cooling the battery to the discharge temperature TD.
  • the temperature TD is preferably variable during step ii). It can for example decrease from a temperature Tomax to a temperature Tomin, it being understood that the charging temperature Te (in °C) is strictly greater than T Dmax and T D min (in °C).
  • the cooling can be carried out by stopping the heating implemented at the end of step i) (i.e. after obtaining a state of charge of approximately 95%) or by forced cooling, and preferably by stopping the heating means implemented at the end of step i).
  • Cooling is generally done at low current (period commonly referred to as the "floating period").
  • the forced cooling can be carried out using at least one of the following cooling means: use of cold pulsed air, or use of a cooling liquid circuit.
  • the method may further comprise the repetition of steps i) and ii) (i.e. carrying out several charge-discharge cycles).
  • the method may further comprise before step i) a step io) of discharging the lithium battery at a discharge temperature TD (in °C), the charging temperature Te (in °C) of step i ) is strictly greater than the discharge temperature TD (in °C) of step io).
  • This embodiment is used when the battery is initially charged.
  • the charging temperatures Ten during the charging steps can be identical or different, and preferably identical.
  • the solid or quasi-solid electrolyte of the battery implemented in the method of the invention preferably comprises one or more polymer materials.
  • the polymer material (or the polymer materials when there are several of them) of the solid or quasi-solid electrolyte preferably represent(s) at least 30% by mass approximately, and in a particularly preferred manner at least 40% by mass approximately , relative to the total mass of the solid or quasi-solid electrolyte.
  • the solid or quasi-solid electrolyte can be a polymer electrolyte comprising:
  • the polymer material based on poly(ethylene oxide) (POE) can be chosen from a polystyrene-poly(ethylene oxide) (PS-b-POE) block copolymer, a polystyrene-poly(ethylene oxide) block copolymer ethylene)-polystyrene (PS-b-POE-b-PS), a poly(ethylene oxide-stat-propylene oxide) random copolymer (i.e. POE-stat-PPO), a poly(ethylene oxide-stat-PPO) random copolymer (i.e. POE-stat-PBO), a poly(ethylene oxide), and a mixture thereof.
  • PS-b-POE polystyrene-poly(ethylene oxide) block copolymer
  • PS-b-POE-b-PS poly(ethylene oxide-stat-propylene oxide) random copolymer
  • POE-stat-PPO poly(ethylene oxide-stat-PPO) random copolymer
  • the lithium salt used in association with the polymer material based on poly(ethylene oxide) can be chosen from lithium fluorate (LiFOs), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPFe), lithium fluoroborate (UBF4), lithium metaborate (UBO2), lithium perchlorate (UCIO4), lithium nitrate (UNO3), lithium bis(fluorosulfonyl)imide (LiFSI), bis (pentafluoroethylsulfonyl) lithium imide (LiBETI), LiAsFe, UCF3SO3, LiSbFe, LiSbCle, LizTiCle, LizSeCle, U2B10CI10, U2B12CI12, lithium bis(oxalato)borate (LiBOB), and a mixture thereof.
  • LiFOs lithium fluorate
  • LiTFSI lithium bis(trifluo
  • the lithium salt preferably represents from 5 to 30% by weight, and even more preferably from 10 to 25% by weight, relative to the total weight of the polymer electrolyte.
  • Said polymeric material based on poly(ethylene oxide) (POE) can be combined with a reinforcing agent. This thus makes it possible to modulate the mechanical properties of the polymer material.
  • Said reinforcing agent is preferably chosen from cellulose nanofibrils, ceramic nanoparticles such as nanoparticles of titanium oxide, aluminum oxide or silicon oxide, and fluorinated polymers and copolymers such as polyfluoride vinylidene (PVdF) or vinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP).
  • PVdF polyfluoride vinylidene
  • PVdF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • the anionic polymer substituted by an anion of a lithium salt may be a block copolymer comprising at least a first block based on poly(ethylene oxide) and at least a second block based on an anionic polymer capable of be prepared from one or more monomers substituted with the anion of a lithium salt, such as sulfonyl (trifluoromethylsulfonyl) imide (TFSILi).
  • TFSILi sulfonyl (trifluoromethylsulfonyl) imide
  • the block copolymer comprising at least a first block based on poly(ethylene oxide) and at least a second block based on an anionic polymer capable of being prepared from one or more monomers substituted by the anion of a lithium salt already includes anionic functions (anion of a lithium salt directly grafted into the structure of the polymer material).
  • the polymer electrolyte then preferably does not comprise any additional lithium salt(s).
  • the monomer or monomers are preferably chosen from vinyl monomers and derivatives.
  • the polymer electrolyte may further comprise at least one non-aqueous plasticizer or solvent. This thus makes it possible to form a gelled polymer electrolyte.
  • the solvent or plasticizer can be chosen from linear and cyclic carbonates such as propylene carbonate, ethylene carbonate or dimethyl carbonate; fluorinated carbonates such as fluoroethylene carbonate; nitriles such as succinonitrile; lactones such as ⁇ -butyrolactone; liquid linear or cyclic polyethers; fluorinated polyethers; sulfur solvents such as sulfolane and dimethyl sulfoxide; and a mixture thereof.
  • linear and cyclic carbonates such as propylene carbonate, ethylene carbonate or dimethyl carbonate
  • fluorinated carbonates such as fluoroethylene carbonate
  • nitriles such as succinonitrile
  • lactones such as ⁇ -butyrolactone
  • liquid linear or cyclic polyethers fluorinated polyethers
  • sulfur solvents such as sulfolane and dimethyl sulfoxide
  • dimethyl ether polyethylene glycol dimethyl ether (or PEGDME) such as tetraethylene glycol dimethyl ether (TEGDME), dioxolane, ethylene carbonate (EC), propylene carbonate (PC ), dimethylcarbonate (DMC), diethylcarbonate (DEC), methyl-isopropyl carbonate (MiPC), ethyl acetate, ethyl butyrate (EB), or a mixture thereof.
  • PEGDME polyethylene glycol dimethyl ether
  • TEGDME tetraethylene glycol dimethyl ether
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethylcarbonate
  • DEC diethylcarbonate
  • MiPC methyl-isopropyl carbonate
  • EB ethyl butyrate
  • the solvent or plasticizer represents from 10% to 70% by mass approximately, even more preferably from 20% to 60% by mass approximately, relative to the total mass of the polymer electrolyte.
  • the solid or quasi-solid electrolyte, the positive electrode, and the negative electrode are preferably in the form of films.
  • the thickness of the films which constitute the various elements of the battery is generally of the order of 1 to a hundred micrometers.
  • the solid or quasi-solid electrolyte film has a thickness of 1 to 50 ⁇ m, and preferably 2 to 20 ⁇ m.
  • the solid or quasi-solid electrolyte can be prepared by any technique known to those skilled in the art such as for example by coating, by extrusion or by pressing (cold or hot).
  • the positive electrode may include a positive electrode active material, optionally an electronic conductivity generating agent, and optionally a polymeric material.
  • the active material of the positive electrode is a reversible active material of lithium ions. In other words, it can reversibly insert or de-insert lithium ions.
  • a metal oxide such as for example a vanadium oxide Ox (2
  • the process of the invention is particularly suitable for LMP batteries, very particularly for LMP batteries in which the active material of the positive electrode is chosen from iron phosphate and its derivatives, in particular LiFePO4.
  • the agent generating electronic conductivity can be chosen from carbon blacks, carbon SP, acetylene blacks, fibers and nanofibers of carbon, carbon nanotubes, graphene, graphite, metallic particles and fibers of at least one conductive metal such as aluminium, platinum, iron, cobalt and nickel, and one of their mixtures .
  • the active material of the positive electrode can represent from 60 to 95% by mass approximately, and preferably from 70 to 90% by mass approximately, relative to the total mass of the positive electrode.
  • the agent generating an electronic conductivity can represent from 0.1 to 10% by mass approximately, and preferably from 0.3 to 5% by mass approximately, relative to the total mass of the positive electrode.
  • the polymer material may be a material chosen from ethylene homopolymers and copolymers; propylene homopolymers and copolymers; homopolymers and copolymers of ethylene oxide (e.g. POE, POE copolymer), of methylene oxide, of propylene oxide, of epichlorohydrin, of allylglycidyl ether, and mixtures thereof; halogenated polymers such as homopolymers and copolymers of vinyl chloride, vinylidene fluoride (PVdF), vinylidene chloride, ethylene tetrafluoride, or chlorotrifluoroethylene, copolymers of vinylidene fluoride and hexafluoropropylene (PVdF- co-HFP) or mixtures thereof; electronic non-conductive polymers of anionic type such as poly(styrene sulfonate), poly(acrylic acid), poly(glutamate), alginate, pectin, gelatin or mixtures thereof
  • anionic polymers substituted by an anion of a lithium salt are as defined in the invention.
  • the polymer material may in particular be a polymer material based on poly(ethylene oxide) (POE) or an anionic polymer substituted by an anion of a lithium salt.
  • the polymer material may represent from 1 to 20% by mass approximately, and preferably from 5 to 15% by mass approximately, relative to the total mass of the positive electrode.
  • the active material of the positive electrode is coated with a layer of carbon.
  • the presence of the carbon layer makes it possible to improve the interface: active material-polymer material.
  • the carbon coating the active material preferably represents from 0.1 to 5% by mass approximately, relative to the mass of active material.
  • the carbon layer is preferably in the form of a layer with a thickness varying from approximately 1 to 4 nm.
  • the positive electrode may further comprise a lithium salt.
  • the lithium salt can be as defined in the invention.
  • the lithium battery may further comprise a current collector connected to the positive electrode.
  • the current collector is generally made of a sheet of metal.
  • the current collector is preferably a stainless steel or aluminum current collector, optionally covered with a carbon-based layer (anti-corrosion layer).
  • the negative electrode is preferably made of metallic lithium, or of one of its alloys such as a lithium alloy with silicon, tin, aluminum or even germanium.
  • the battery is then preferably an LMP battery.
  • a second object of the invention is the use of a lithium battery chosen from lithium batteries with solid or quasi-solid electrolyte operating with a charging temperature Te and a discharging temperature TD so that the charging temperature Te is strictly higher than the discharging temperature TD, to improve its resistance to cycling.
  • the lithium battery, the charging temperature Te, and the discharging temperature TD are as defined in the first object of the invention.
  • the lithium battery as defined in the first object of the invention is characterized in that it has a charging temperature Te and a discharging temperature TD and in that the charging temperature Te is strictly higher than the temperature of discharge TD, the charging temperature Te and the discharging temperature TD being as defined in the first object of the invention.
  • the present invention is illustrated by the following exemplary embodiments, to which it is however not limited.
  • FIG. 1 represents the faradic efficiency (in percentage) as a function of the number of cycles (in number) when the battery operates according to a method in accordance with the invention and according to a method of the prior art.
  • Example 1 preparation of an LMP battery and operation of such an LMP battery
  • a positive electrode in the form of a film was prepared as follows: a mixture of 46 g of LiFePC, 1.2 g of carbon black, 17.5 g of homo-POE polymer material, 6.5 g of deionized water were introduced into a mixer sold under the trade name Plastograph® by the company Brabender®. The mixing was carried out at 60° C. at 80 revolutions per minute.
  • the paste thus obtained was then rolled at 60° C. on a carbon-coated aluminum current collector.
  • the film obtained was dried for 10 minutes at 100° C. before being used.
  • the positive electrode obtained comprises 71% by mass of LFP active material, 27% by mass of homo-POE polymer material and 1.9% by mass of carbon black. It has a thickness of approximately 45 ⁇ m.
  • An LMP battery was prepared by assembly under a controlled atmosphere (dew point -50°C):
  • a film of solid polymer electrolyte 50 ⁇ m thick comprising 80 g of polymer material (homo-POE and PVDF-co-HFP mixture) and 20 g of LiTFSI,
  • the lithium sheet and the film of solid polymer electrolyte are laminated at 70°C and at 5 bars to ensure good Li/electrolyte contacts, then finally the positive electrode is laminated at 70°C and at 5 bars on the Li/electrolyte assembly to form the battery.
  • the electrolyte film is disposed between the lithium metal film and the positive electrode film.
  • One lead wire is connected to the lithium and another lead wire is connected to the positive electrode current collector.
  • the lithium battery obtained has a structure of the sandwich type and it is confined under vacuum in a pouch (well known according to the Anglicism “coffee bag”) which corresponds to a heat-sealable waterproof packaging to protect it from humidity.
  • a lithium battery under a pressure of 1 bar is obtained.
  • the battery obtained in point 1.2 was tested in an uncontrolled atmosphere.
  • the lithium battery is then subjected to several charge-discharge processes (i.e. several repeated steps i) and ii), the charging step i) being carried out at a charging temperature Te of 90° C. and the step ii ) discharging being carried out at a discharging temperature TD of 50° C. (process according to the invention).
  • charge-discharge processes i.e. several repeated steps i) and ii
  • the charging step i) being carried out at a charging temperature Te of 90° C.
  • the step ii ) discharging being carried out at a discharging temperature TD of 50° C.
  • Step i) is carried out using a Memmert UNE500 oven.
  • Figure 1 shows the faradic efficiency (in percentage) as a function of the number of cycles (in number) for the lithium battery operating according to a method of the invention (curve with the solid circles), and by comparison for the lithium battery not operating according to a method of the invention (curve with solid squares).
  • the first cycle is carried out at C/10 (charge in 10 hours) and D/(10) (discharge in 10 hours) and the following cycles at C/4 (charge in 4 hours) and D/20 (discharge in 20 hours ).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
EP22801726.5A 2021-10-06 2022-10-05 Verfahren zum betrieb einer lithiumbatterie Pending EP4413630A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2110587A FR3127847B1 (fr) 2021-10-06 2021-10-06 procédé de fonctionnement d’une batterie au lithium
PCT/EP2022/077643 WO2023057486A2 (fr) 2021-10-06 2022-10-05 Procédé de fonctionnement d'une batterie au lithium

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Publication Number Publication Date
EP4413630A2 true EP4413630A2 (de) 2024-08-14

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US (1) US20240380014A1 (de)
EP (1) EP4413630A2 (de)
JP (1) JP2024536045A (de)
KR (1) KR20240089364A (de)
CN (1) CN118120095A (de)
AU (1) AU2022361674A1 (de)
CA (1) CA3232453A1 (de)
FR (1) FR3127847B1 (de)
WO (1) WO2023057486A2 (de)

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CN103746150B (zh) * 2013-12-31 2017-02-08 曙鹏科技（深圳）有限公司 磷酸铁锂电池系统
US20210159557A1 (en) * 2019-11-25 2021-05-27 Alan C. Knudson Battery charge and discharge temperature control system

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JP2024536045A (ja) 2024-10-04
WO2023057486A2 (fr) 2023-04-13
US20240380014A1 (en) 2024-11-14
FR3127847B1 (fr) 2024-07-26
FR3127847A1 (fr) 2023-04-07
AU2022361674A1 (en) 2024-03-28
CA3232453A1 (fr) 2023-04-13
WO2023057486A3 (fr) 2023-06-01
CN118120095A (zh) 2024-05-31

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