EP3235022A1 - Lithium accumulator with a two-layered thermally insulating package and with a heat pipe for thermal management - Google Patents

Lithium accumulator with a two-layered thermally insulating package and with a heat pipe for thermal management

Info

Publication number
EP3235022A1
EP3235022A1 EP15810636.9A EP15810636A EP3235022A1 EP 3235022 A1 EP3235022 A1 EP 3235022A1 EP 15810636 A EP15810636 A EP 15810636A EP 3235022 A1 EP3235022 A1 EP 3235022A1
Authority
EP
European Patent Office
Prior art keywords
package
heat pipe
electrochemical
accumulator according
cell
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.)
Withdrawn
Application number
EP15810636.9A
Other languages
German (de)
French (fr)
Inventor
Fabien PERDU
Lionel Picard
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.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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 Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Publication of EP3235022A1 publication Critical patent/EP3235022A1/en
Withdrawn legal-status Critical Current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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6552—Closed pipes transferring heat by thermal conductivity or phase transition, e.g. heat pipes
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6556—Solid parts with flow channel passages or pipes for heat exchange
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
    • 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
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/117—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/117—Inorganic material
    • H01M50/119—Metals
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
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    • H01M50/121—Organic material
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    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/122—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
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    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
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    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H01M50/1243—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure characterised by the internal coating on the casing
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    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
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    • H01M50/1245—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure characterised by the external coating on the casing
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    • H01M50/131—Primary casings, jackets or wrappings of a single cell or a single battery characterised by physical properties, e.g. gas-permeability or size
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    • H01M50/14—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors
    • H01M50/143—Fireproof; Explosion-proof
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H—ELECTRICITY
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    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
    • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
    • H01M50/222—Inorganic material
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
    • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
    • H01M50/222—Inorganic material
    • H01M50/224—Metals
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    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
    • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
    • H01M50/227—Organic material
    • H—ELECTRICITY
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    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
    • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
    • H01M50/229—Composite material consisting of a mixture of organic and inorganic materials
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
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    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • 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
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/296—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by terminals of battery packs
    • H—ELECTRICITY
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6569—Fluids undergoing a liquid-gas phase change or transition, e.g. evaporation or condensation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of lithium electrochemical generators, which operate according to the principle of insertion or deinsertion, or in other words intercalation-deintercalation, of lithium in at least one electrode.
  • the invention particularly relates to a lithium electrochemical accumulator, in particular lithium-ion battery whose packaging is mechanically resistant and fireproof and thermally insulating, and whose thermal management is provided by a heat pipe, both in normal operation and in case of abnormal operation of the cell (s) electrochemical (s) of the accumulator.
  • a lithium battery or accumulator usually comprises one or more electrochemical cells each consisting of an electrolyte constituent between a positive electrode or cathode and a negative or anode electrode, a current collector connected to the cathode, a current collector connected to a the anode and finally a package arranged to contain the electrochemical cell (s) with sealing while being traversed by a portion of the current collectors.
  • the primary function of a package is to separate the inside of the battery from the outside.
  • the electrolyte of an electrochemical cell must never come into contact with traces of moisture, at the risk of producing hydrofluoric acid and greatly degrading the performance of the cell.
  • a package must also withstand high mechanical stresses coming either from the outside (shocks, vibrations) or from the inside (pressure in case of failure of the electrochemical cell).
  • a packaging also has thermal protection functions: it must allow the battery to withstand an external fire sufficiently long. Furthermore, it must be avoided that the thermal runaway of a cell can spread to neighboring cells, or a module grouping several cells to neighboring modules.
  • the cell (s) in normal operation gives off the heat that must be discharged outside the packaging, in order to avoid excessive temperature inside the packaging.
  • the existing battery packs are most often metallic and rigid or flexible and in the form of laminated layers.
  • the existing packages of module and battery-pack with several modules are most often metallic and rigid. In all these cases, the packages are thermally conductive, which is favorable in terms of operating conditions but unfavorable in terms of safety in the event of abnormal operation of the cell (s).
  • a heat pipe consists of a sealed enclosure containing a heat transfer fluid which absorbs heat by vaporizing in an area called heated zone or evaporator, and restores it by liquefying in another zone called cooled zone or condenser.
  • a heat pipe allows to passively exchange heat flows two orders of magnitude higher than the best metals in the same geometry.
  • FIG. 1A describes a battery 100 according to this patent application by using new numerical references.
  • This battery 100 comprises a housing and a plurality of electrochemical cells C arranged in the lower compartment 301 of the housing.
  • the electrochemical cells are cooled by pulsed heat pipes 201 and are in contact with the heated zone 240 of the heat pipes.
  • the cooled zone 230 of these pulsed heat pipes 201 is in the upper housing compartment which comprises a phase change material with high thermal inertia.
  • the upper housing compartment is connected to a heatsink not shown.
  • the patent application FR 2989323 A1 describes a battery module comprising cells arranged in a compartment, these cells being in direct contact with heat pipes operating by capillarity.
  • the cooled zone of each heat pipe is integrated in a matrix with a phase change material.
  • the phase change material is in contact with a heat sink.
  • the patent application US 2011/0206965 A1 describes a battery with a plurality of electrochemical cells and heat pipes inserted between two individual cells, the cells and heat pipes being all arranged in the same housing.
  • the cooled zone of each heat pipe is equipped with fins to improve the cooling and to homogenize the temperature inside the housing.
  • the patent application US 2011/0000241 A1 describes a battery with a plurality of electrochemical cells and an associated heat pipe, arranged in the same housing, the cooled zone of the heat pipe being connected to an active cooling device which is a heat exchanger. .
  • the patent application FR 2,539,919 describes a battery 100, reproduced in FIG. 1B, comprising a plurality of electrochemical cells C arranged inside a thermal protection envelope 300 and a heat pipe 200.
  • the heated zone 240 of the heat pipe located inside the casing 300 while being heated by a catalytic converter.
  • the heat pipe brings heat from outside to the electrochemical cells C which in this case use double chloride of sodium and aluminum (NaAICU) as the electrolyte and which require high operating temperatures, typically between 300 ° C and 400 ° C.
  • the disclosed heat pipe 200 only serves to heat the electrochemical cells and is not intended to evacuate the heat inside the package.
  • FR 2 539 919 does not disclose in any case a cooling system of the electrochemical cells.
  • Nothing in this application relates to the thermal management of a lithium battery which differs from that of a NaAICLt accumulator since it must be provided with heat and not cool in operation.
  • the object of the invention is to respond at least in part to this need.
  • an electrochemical lithium battery comprising at least a first package housing at least one electrochemical cell, said first package comprising at least:
  • the outer layer being mechanically resistant and fire-resistant
  • a cooling device comprising at least one heat pipe whose enclosure passes through the first package (s) in a sealed manner and that the heated zone of the heat pipe (s) is located at inside the first package (s) and that the cooled area of the heat pipe (s) is located outside the first package (s).
  • the term "heated zone of a heat pipe” denotes the usual technological meaning, namely the zone of the heat pipe where the heat transfer fluid of the heat pipe receives heat and evaporates.
  • the heated zone is still usually called an evaporator.
  • the term "cooled zone of a heat pipe” also refers to the usual technological meaning, namely the zone of the heat pipe where the heat transfer fluid of the heat pipe transmits heat and condenses.
  • the cooled zone is still usually called a condenser.
  • the accumulator according to the invention can house one or more electrochemical cells in a first package.
  • a package according to the invention fulfills two functions: a function of mechanical protection and fire resistance, and a thermal insulation function.
  • the thermal insulation must be sufficient to allow the electrochemical cell (s) to be protected from extreme heat outside, which can be caused in particular by the abnormal operation of a neighboring electrochemical cell outside. .
  • ABSO "Abnormal operation” means an increase in temperature and pressure beyond that expected in normal operation, which is large enough to cause degradation of the cell and / or thermal runaway of the ) cell (s) around.
  • the cooling device is adapted to evacuate the heat confined by the inner layer inside the accumulator even in case of abnormal operation of the electrochemical cell.
  • Thermal management of the accumulator in normal or abnormal operation is therefore ensured by the cooling device.
  • a heat pipe implemented in the invention comprises the following elements:
  • a diphasic fluid inside the tubular casing, at the temperature of use such as, for example, water, ammonia, methanol, ethanol, acetone, toluene, heptane, .
  • a porous capillary medium such as a sintered metal cloth or powder, or grooves inside the tubular envelope.
  • the diameter of the heat pipe according to the invention is of the order of a few millimeters, preferably between 1 mm and 2 cm, more preferably between 2 mm and 2 cm. and 6 mm.
  • the length of the heat pipe can be arbitrary, since it affects only very little thermal evacuation.
  • the heat pipe may protrude from the package of 1 mm to 2 cm.
  • the thermal conductivity K of the inner layer is less than 0,05W.m " ⁇ K" 1.
  • a very low thermal conductivity of the inner layer makes it possible to confine with great efficiency the internal heat of the packaging according to the invention, in the event of abnormal operation of an electrochemical cell or to protect it from heat external to the packaging. .
  • the outer layer provides fire resistance according to the SAE J2464 standard.
  • the Young's modulus E of the outer protective layer is greater than 1GPa.
  • the cooled zone of the heat pipe is located above the first package, the heat pipe thus constituting a thermosiphon or heat pipe assisted by gravity.
  • a diphasic thermosiphon is a heat pipe that transfers heat by evaporation / condensation of a fluid inside an envelope without any capillary structure, that is to say with a gravity return of gravity inside the envelope.
  • a gravity-assisted heat pipe [1] is a heat pipe in which there is a capillary structure, usually grooves, but the return of condensates from the condenser to the evaporator is ensured by the gravity, the evaporator of the heat pipe being at a position lower than the condenser.
  • the capillary structure is therefore not intended to reduce the condensates; but to improve the exchange coefficients in evaporation and condensation, and to push back the training limit.
  • At least one heat pipe constitutes a current output terminal of the accumulator. This advantageously makes it possible to dispense with a welding step of an output terminal on a part of the accumulator, as in the accumulators according to the state of the art.
  • the (the) heat pipe (s) is (are) adapted (s) to limit or even eliminate the liquid phase within its (their) enclosure in case of abnormal operation of the cell (s) (s) ) electrochemical (s) from which it (s) receives (wind) heat at its (their) heated zone.
  • a heat pipe configured in such a manner has a saturation phenomenon as illustrated in FIG. 2: when the temperature becomes too great, the heat pipe is dimensioned so that the liquid phase evaporates completely.
  • the amount of heat transmitted by the heated zone to the cooled zone of the heat pipe reaches a maximum that does not increase significantly beyond the saturation temperature, which is chosen as the abnormal operating temperature of a cell. electrochemical. Excessive heat is thus completely confined by the packaging and the heat pipe.
  • the inner layer comprises a thermosetting or thermoplastic polymer matrix, this matrix being mainly loaded with silica airgel or other particulate filler.
  • the material constituting the matrix of the inner layer is preferably chosen from urethane, acrylate, methacrylate, polyether and silicone, or is a vinylic polymer, in particular styrene, a polyolefin polymer which may or may not be crosslinked, a polymer of the type unsaturated polyester or an epoxy resin.
  • the outer protective layer comprises a thermosetting matrix in which is embedded a fibrous reinforcement.
  • the material constituting the matrix of the outer layer may advantageously be chosen from urethane, acrylate or methacrylate, or it may be a vinylic polymer, especially styrene, an unsaturated polyester polymer or an epoxy resin.
  • the material constituting the fibrous reinforcement may advantageously be short or long fibers, preferably glass fibers, carbon, an aromatic polyamide, silicon carbide SiC, bamboo fibers, flax, coconut fibers or hemp fibers. .
  • the enclosure (s) of the heat pipe (s) may be of circular or prismatic section.
  • a heat pipe with such a chamber section may optionally be adapted to serve as a winding mandrel of a cell.
  • the electrochemical cell C is in the form of a coil wound around the enclosure of the heat pipe.
  • the enclosure of at least one heat pipe is arranged on the periphery of the electrochemical cell (s) C in a gap inside the first package.
  • the electrochemical accumulator comprises a plurality of a number of n first packages, of which a number equal to n-1 of the first Each package houses an electrochemical cell, the (n-1) first packages being themselves housed inside the other first package.
  • the accumulator comprises a second metal alloy package, such as an aluminum alloy, housing the electrochemical cell (s), the second package being itself even housed tightly in the first package.
  • the invention can be applied to metal alloy packaging batteries according to the state of the art.
  • the first package comprises, on the inner layer, an electrically conductive coating.
  • the electrically conductive coating may preferably be based on photon sintered metal particles or conductive graphites, preferably deposited as a paint or aerosol. Its role is to ensure the electromagnetic compatibility of the battery.
  • the first package has on its inner face, a coating with a barrier function, adapted to ensure the chemical neutrality of the inner layer vis-à-vis the electrolyte of the electrochemical cell C
  • the material of the barrier coating may be chosen from polypropylene, polyethylene, a polymer of the polyaryletherketone (PAEK) family, preferably polyetheretherketone (PEEK TM), or a polymer of the polyimide family.
  • PAEK polyaryletherketone
  • PEEK TM polyetheretherketone
  • FIG. 1A represents a lithium-ion accumulator with a cooling device according to the state of the art
  • FIG. 1B represents a NaAICU accumulator according to the state of the art
  • FIG. 2 illustrates the phenomenon of saturation of a heat pipe
  • FIG. 3 schematically illustrates the relative arrangement between the package in which an electrochemical cell is housed and a heat pipe of a lithium-ion accumulator according to the invention
  • FIG. 4 illustrates an exemplary embodiment of a lithium-ion battery according to the invention
  • FIG. 5 illustrates another exemplary embodiment of a lithium-ion battery according to the invention
  • FIG. 6 illustrates yet another embodiment of a lithium-ion battery according to the invention
  • FIG. 7 illustrates yet another embodiment of a lithium-ion battery according to the invention.
  • the accumulator 1 As represented in FIG. 3, the accumulator 1 according to the invention comprises a package 3 which houses at least one lithium electrochemical cell.
  • the package 3 comprises an outer layer 4 superimposed on an inner layer 5, thermally insulating.
  • the outer layer 4 is mechanically resistant and provides fire resistance.
  • the outer layer 4 is preferably epoxy resin polymer, polyurethane resin, polyvinyl resin, polyester resin, optionally with reinforcements of the glass fiber type or carbon fiber.
  • the thickness of the layer 4 is preferably between 300 ⁇ and 2 mm, more preferably of the order of 1 mm.
  • the inner layer 5 is preferably made of polyethylene (PE) or of polypropylene (PP), or of PTFE or of PFE, with possibly thermally insulating fillers of the type
  • the thickness of the layer 5 is preferably less than 300 ⁇ preferably and greater than 20 nanometers (nm).
  • a coating 6 covers the inner layer 5. This coating 6 may have different functions as explained below.
  • the cooling device of the accumulator 1 comprises a heat pipe 2 comprising a sealed enclosure 21, inside which circulates a coolant 22.
  • This heat transfer fluid is adapted to operate in linear mode at the operating temperature of a cell electrochemical lithium, and can typically be water.
  • the heat pipe 2 passes through the package 3 in a sealed manner.
  • the heated zone 24 is located within the package 3.
  • the cooled zone 23 is located outside the package 3.
  • the diameter of the heat pipe 2 is of the order of a few millimeters, preferably between 1 mm and 2 cm, more preferably between 2 and 6 mm.
  • the length of heat pipe can be any, since it affects very little thermal evacuation.
  • the heat pipe may protrude from the package of 1 mm to 2 cm.
  • FIG. 4 An exemplary embodiment of the invention is shown in FIG. 4.
  • a single electrochemical cell C is arranged inside the first package 3.
  • the electrochemical cell is in the form of a coil wound around the heat pipe 2
  • the enclosure 21 of the heat pipe 2 has a circular section.
  • the positive 7 and negative 8 terminals also pass through the package 3 sealingly. According to one variant, it is possible to use the heat pipe itself as the output terminal of the current of the accumulator.
  • the coating 6 ensures the neutrality of the inner layer 5 vis-à-vis the electrolyte of the electrochemical cell C.
  • the first package 3 being very thermally insulating, with a thermal conductivity of the inner layer less than 0.05 Wm ⁇ .K "1 , the thermal management in normal operation of the cell 6 is provided by the heat pipe 2.
  • the heated zone 24 is inside the hollow cylinder formed by the cell C wound on itself, and in thermal contact therewith. Thus, a large amount of heat is transmitted from the cell C to the heated zone 24.
  • the heat transfer fluid 22 then follows an evaporation and condensation cycle: it evaporates at the heated zone 24, and condenses at the level of the cooled zone 23.
  • This cooled zone 23 may optionally comprise a thermal diffuser in order to evacuate the heat transmitted during the condensation of the fluid 22.
  • the heated zone 24 being located below the zone 23, the heat pipe 2 constitutes a thermosiphon and operates thanks to gravity: the condensed fluid falls by gravity to the heated zone 23 where it undertakes a new evaporation cycle and condensation.
  • the inner layer 5 confines the heat inside the package 3.
  • a heat pipe has a saturation limit as shown in FIG. 5. Beyond a certain temperature, it stops transmitting heat. Thus, in the event of abnormal operation of the cell C, the heat is also not transmitted by the heat pipe 2. The heat is thus effectively confined within the package 3 according to the invention.
  • the inner layer 5 prevents degradation of the electrochemical cell C or in other words, protects the electrochemical accumulator 1.
  • the accumulator illustrated in FIG. 3 is made by winding around the enclosure of the heat pipe 2 the electrochemical cell C.
  • the enclosure 21 of the heat pipe 2 is thus adapted to serve as a mandrel during the manufacture of the cell.
  • thermoplastic polymer a thermoplastic polymer and a low load K.
  • thermoplastic-thermosetting bi-material injection process can be envisaged for producing the two layers 4, 5, in a single step.
  • the positive 7 and negative 8 terminals may already be present at the beginning of the injection process. It is conceivable to produce the layers 4, 5 by the injection method described and claimed in the patent application FR 14 51546 in the name of the applicant.
  • This example consists in the creation of two half-shells which will be gathered around the electrochemical cell C.
  • the introduction of the electrolyte is made at the time of the gathering of the two half-shells by injection before plastic welding / final bonding.
  • thermosetting material thermosetting areas to ensure homogeneity of reinforcement for fire resistance and mechanical reinforcement.
  • the accumulator 1 comprises a plurality of electrochemical cells C.
  • Each electrochemical cell is arranged in a sealed manner within a package 3 'according to FIG. state of the art.
  • This 3 'package is metal alloy type, such as aluminum alloy, or plastic.
  • This packaging 3 'according to the state of the art is housed in a sealed manner in the package 3 according to the invention.
  • Several heat pipes 2 pass tightly through the package 3 and have one of their ends arranged in interstices 9 within the package 3. Their heated zones 24 are thus in contact with the packages 3 'according to the state of the package. art, which are thermally conductive and thus which diffuse the heat released by the electrochemical cells C.
  • the thermal contact between a heated zone 24 of heat pipe and the 3 'packaging of an electrochemical cell can be improved by interposing thermally conductive grease .
  • an electrically conductive coating 6 covers the inside of the inner layer 5 of the package 3, in order to ensure the electromagnetic compatibility of the battery.
  • the inner layer 5 confines the heat inside the package 3. Similarly, in case of heat outside the high packaging 3, the inner layer 5 prevents degradation electrochemical cells C and thus protects the electrochemical accumulator 1.
  • Other variants and improvements may be envisaged without departing from the scope of the invention.
  • FIG. 6 it is possible to envisage an embodiment of an accumulator with several electrochemical cells C immersed in the same electrolyte in the package 3 according to the invention.
  • FIG. 6 Such a mode is illustrated in FIG. 6, in which three cells arranged in parallel in the same package 3 are seen, with a single heat pipe 2 of pulsed type, the heated zones 24 of which are inside and its cooled zones 23 at the same time. outside.
  • This embodiment is particularly advantageous when it is desired to produce C cells of very large capacity.
  • the electrochemical accumulator comprises a plurality of a number of n first packagings, of which a number equal to n-1 of the first packs each houses an electrochemical cell C, the (n -1) first packs being themselves housed inside the other first packaging.
  • This mode is illustrated in FIG. 7, in which we see two cells arranged in parallel and each inside a package 3 according to the invention, a central heat pipe 2 being arranged between these two packages 3 themselves housed in a third peripheral package 3.

Abstract

Lithium electrochemical accumulator including at least one first package housing at least one electrochemical cell, said first package including at least: one internal thermally insulating layer suitable for confining, to the interior of a first package, the heat given off even in case of abnormal operation of a cell C and for protecting the cell(s) from heat generated outside the first package; one external layer superposed on the internal layer, the external layer being mechanically strong and fire resistant; and one cooling device including at least one heat pipe the enclosure of which passes through the first package(s) in a seal-tight manner and such that the heated zone of the heat pipe(s) is located inside the first package(s) and that the cooled zone of the heat pipe(s) is located outside the first package(s).

Description

ACCUMULATEUR AU LITHIUM AVEC EMBALLAGE ISOLANT  LITHIUM ACCUMULATOR WITH INSULATING PACKAGING
THERMIQUEMENT A DEUX COUCHES ET AVEC CALODUC POUR LA THERMALLY TWO LAYERS AND WITH HEAT PUMP FOR
GESTION THERMIQUE THERMAL MANAGEMENT
Domaine technique  Technical area
La présente invention concerne le domaine des générateurs électrochimiques au lithium, qui fonctionnent selon le principe d'insertion ou de désinsertion, ou autrement dit intercalation-désintercalation, de lithium dans au moins une électrode.  The present invention relates to the field of lithium electrochemical generators, which operate according to the principle of insertion or deinsertion, or in other words intercalation-deintercalation, of lithium in at least one electrode.
L'invention concerne en particulier un accumulateur électrochimique au lithium, en particulier au lithium-ion dont l'emballage est résistant mécaniquement et au feu et isolant thermiquement, et dont la gestion thermique est assurée par un caloduc, tant en fonctionnement normal qu'en cas de fonctionnement anormal de la (des) cellule(s) électrochimique(s) de l'accumulateur.  The invention particularly relates to a lithium electrochemical accumulator, in particular lithium-ion battery whose packaging is mechanically resistant and fireproof and thermally insulating, and whose thermal management is provided by a heat pipe, both in normal operation and in case of abnormal operation of the cell (s) electrochemical (s) of the accumulator.
Art antérieur  Prior art
Une batterie ou accumulateur au lithium comprend usuellement une ou plusieurs cellules électrochimiques constituées chacune d'un constituant d'électrolyte entre une électrode positive ou cathode et une électrode négative ou anode, un collecteur de courant connecté à la cathode, un collecteur de courant connecté à l'anode et enfin, un emballage agencé pour contenir la(les) cellule(s) électrochimique(s) avec étanchéité tout en étant traversé par une partie des collecteurs de courant.  A lithium battery or accumulator usually comprises one or more electrochemical cells each consisting of an electrolyte constituent between a positive electrode or cathode and a negative or anode electrode, a current collector connected to the cathode, a current collector connected to a the anode and finally a package arranged to contain the electrochemical cell (s) with sealing while being traversed by a portion of the current collectors.
La fonction première d'un emballage est de séparer l'intérieur de l'accumulateur de l'extérieur. L'électrolyte d'une cellule électrochimique ne doit jamais rentrer en contact avec des traces d'humidité, au risque de produire de l'acide fluorhydrique et de fortement dégrader les performances de la cellule.  The primary function of a package is to separate the inside of the battery from the outside. The electrolyte of an electrochemical cell must never come into contact with traces of moisture, at the risk of producing hydrofluoric acid and greatly degrading the performance of the cell.
Un emballage doit également résister à de fortes contraintes mécaniques provenant soit de l'extérieur (chocs, vibrations) soit de l'intérieur (pression en cas de défaillance de la cellule électrochimique).  A package must also withstand high mechanical stresses coming either from the outside (shocks, vibrations) or from the inside (pressure in case of failure of the electrochemical cell).
Un emballage a également des fonctions de protection thermique: il doit permettre à la batterie de résister suffisamment longtemps à un feu extérieur. Par ailleurs, il faut éviter que l'emballement thermique d'une cellule puisse se propager aux cellules voisines, ou d'un module regroupant plusieurs cellules aux modules voisins.  A packaging also has thermal protection functions: it must allow the battery to withstand an external fire sufficiently long. Furthermore, it must be avoided that the thermal runaway of a cell can spread to neighboring cells, or a module grouping several cells to neighboring modules.
L'ensemble de ces contraintes de sécurité nécessite de concevoir un emballage le plus solide, le plus étanche, et le plus isolant thermiquement possible, et ce tout en veillant à ne pas pénaliser la masse et le volume de l'accumulateur. D'autre part, le fonctionnement optimal des cellules en puissance et en vieillissement nécessite une gestion thermique précise: ainsi, si la température interne à l'emballage est trop élevée, la(les) cellule(s) vieillisse(nt) prématurément même sans être sollicitée(s) en fonctionnement. A l'inverse, si la température interne à l'emballage est trop basse, la(les) cellule(s) est (sont) incapable(s) de fournir de la puissance car la résistance électrique est excessive et elle (s) se dégrade(nt) rapidement en charge du fait du dépôt de lithium métal sur l'électrode négative. All of these safety constraints require the design of a strongest package, the most waterproof, and the most thermally insulating possible, and this while being careful not to penalize the mass and volume of the accumulator. On the other hand, the optimal functioning of cells in power and aging requires precise thermal management: thus, if the temperature inside the packaging is too high, the cell (s) age (s) prematurely even without to be solicited (s) in operation. Conversely, if the temperature inside the package is too low, the cell (s) is (are) unable to provide power because the electrical resistance is excessive and it (s) degrade (s) rapidly in charge due to the deposition of lithium metal on the negative electrode.
Par ailleurs, la (les) cellule(s) dégage(nt) en fonctionnement normal de la chaleur qui doit être évacuée en dehors de l'emballage, afin d'éviter une température excessive à l'intérieur de l'emballage.  In addition, the cell (s) in normal operation gives off the heat that must be discharged outside the packaging, in order to avoid excessive temperature inside the packaging.
De nombreuses solutions ont été imaginées pour évacuer la chaleur interne à l'emballage pour éviter un échauffement d'une (de) cellule(s) en fonctionnement normal.  Many solutions have been devised to evacuate the internal heat to the packaging to prevent heating of one (of) cell (s) in normal operation.
Les emballages d'accumulateur existants sont le plus souvent métalliques et rigides ou, souples et sous la forme de couches laminées. Les emballages existants de module et de pack-batterie à plusieurs modules sont le plus souvent métalliques et rigides. Dans tous ces cas, les emballages sont thermiquement conducteurs, ce qui est favorable en termes de conditions de fonctionnement mais défavorable en termes de sécurité en cas de fonctionnement anormal de la (des) cellule(s).  The existing battery packs are most often metallic and rigid or flexible and in the form of laminated layers. The existing packages of module and battery-pack with several modules are most often metallic and rigid. In all these cases, the packages are thermally conductive, which is favorable in terms of operating conditions but unfavorable in terms of safety in the event of abnormal operation of the cell (s).
En ce qui concerne le refroidissement des cellules électrochimiques, elles peuvent être refroidies soit par un flux d'air, soit par un circuit de refroidissement liquide, parfois par des caloducs. Un caloduc est constitué d'une enceinte étanche renfermant un fluide caloporteur qui absorbe de la chaleur en se vaporisant dans une zone dite zone chauffée ou évaporateur, et la restitue en se liquéfiant dans une autre zone dite zone refroidie ou condenseur. Un caloduc permet d'échanger de façon passive des flux de chaleur deux ordres de grandeur supérieurs aux meilleurs métaux dans la même géométrie. On pourra se reporter à la publication [1].  As for the cooling of the electrochemical cells, they can be cooled either by a flow of air, or by a liquid cooling circuit, sometimes by heat pipes. A heat pipe consists of a sealed enclosure containing a heat transfer fluid which absorbs heat by vaporizing in an area called heated zone or evaporator, and restores it by liquefying in another zone called cooled zone or condenser. A heat pipe allows to passively exchange heat flows two orders of magnitude higher than the best metals in the same geometry. We can refer to the publication [1].
Parmi les solutions existantes qui proposent des caloducs pour évacuer efficacement la chaleur de la batterie, on peut citer la demande de brevet CN103367837 A. On reproduit en figure 1A décrit une batterie 100 selon cette demande de brevet en utilisant de nouvelles références numériques. Cette batterie 100, comprend un boîtier et une pluralité de cellules électrochimiques C agencées dans le compartiment inférieur 301 du boîtier. Les cellules électrochimiques sont refroidies par des caloducs puisés 201 et sont en contact avec la zone chauffée 240 des caloducs. La zone refroidie 230 de ces caloducs puisés 201 se trouve dans le compartiment supérieur de boîtier qui comporte un matériau à changement de phase à grande inertie thermique. En outre, le compartiment supérieur de boîtier est relié à un dissipateur thermique non représenté. Among the existing solutions that offer heat pipes to effectively remove the heat from the battery, mention may be made of the patent application CN103367837 A. One reproduces in FIG. 1A describes a battery 100 according to this patent application by using new numerical references. This battery 100 comprises a housing and a plurality of electrochemical cells C arranged in the lower compartment 301 of the housing. The electrochemical cells are cooled by pulsed heat pipes 201 and are in contact with the heated zone 240 of the heat pipes. The cooled zone 230 of these pulsed heat pipes 201 is in the upper housing compartment which comprises a phase change material with high thermal inertia. In addition, the upper housing compartment is connected to a heatsink not shown.
La demande de brevet FR 2989323 Al décrit quant à elles un module de batteries comportant des cellules agencées dans un compartiment, ces cellules étant en contact direct avec des caloducs fonctionnant par capillarité. La zone refroidie de chaque caloduc est intégrée dans une matrice à matériau à changement de phase. Le matériau à changement de phase est en contact avec un dissipateur thermique.  The patent application FR 2989323 A1 describes a battery module comprising cells arranged in a compartment, these cells being in direct contact with heat pipes operating by capillarity. The cooled zone of each heat pipe is integrated in a matrix with a phase change material. The phase change material is in contact with a heat sink.
La demande de brevet US 2011/0206965 Al décrit un accumulateur à pluralité de cellules électrochimiques et de caloducs intercalés individuellement entre deux cellules, les cellules et caloducs étant tous agencés dans un même boîtier. La zone refroidie de chaque caloduc est dotée d'ailettes permettant d'améliorer le refroidissement et d'homogénéiser la température à l'intérieur du boîtier.  The patent application US 2011/0206965 A1 describes a battery with a plurality of electrochemical cells and heat pipes inserted between two individual cells, the cells and heat pipes being all arranged in the same housing. The cooled zone of each heat pipe is equipped with fins to improve the cooling and to homogenize the temperature inside the housing.
La demande de brevet US 2011/0000241 Al décrit quant à elle un accumulateur à pluralité de cellules électrochimiques et un caloduc associé, agencés dans un même boîtier, la zone refroidie du caloduc étant reliée à un dispositif de refroidissement actif qui est un échangeur de chaleur.  The patent application US 2011/0000241 A1 describes a battery with a plurality of electrochemical cells and an associated heat pipe, arranged in the same housing, the cooled zone of the heat pipe being connected to an active cooling device which is a heat exchanger. .
Ces demandes selon l'état de l'art fournissent des solutions aux problématiques liées à la gestion thermique des accumulateurs en fonctionnement normal mais qui ne proposent pas de protection efficace contre une chaleur excessive à l'extérieur d'un emballage.  These requests according to the state of the art provide solutions to the problems related to the thermal management of batteries in normal operation but do not provide effective protection against excessive heat outside a package.
On comprend ainsi que l'ensemble de solutions connues favorisant l'échange thermique intérieur/extérieur est antinomique avec la recherche d'une protection contre le feu, les températures extrêmes, ou la propagation de l'emballement thermique de cellule(s). A l'inverse, l'utilisation de matériaux très isolants contre le feu, les températures extrêmes ou la propagation de l'emballement rend plus difficile le fonctionnement en puissance et en durée de vie de la batterie car la chaleur interne à l'emballage devient plus difficile à évacuer.  It is thus understood that the set of known solutions favoring indoor / outdoor heat exchange is antinomic with the search for protection against fire, extreme temperatures, or the propagation of thermal runaway cell (s). Conversely, the use of highly insulating materials against fire, extreme temperatures or the propagation of runaway makes it more difficult to operate in power and life of the battery because the internal heat to the packaging becomes more difficult to evacuate.
La demande de brevet FR 2 539 919 décrit une batterie 100, reproduite en figure 1B, comprenant une pluralité de cellules électrochimiques C agencées à l'intérieur d'une enveloppe de protection thermique 300 et un caloduc 200. La zone chauffée 240 du caloduc se trouve à l'intérieur de l'enveloppe 300 en étant chauffée par un convertisseur catalytique. Cependant, dans la configuration divulguée, le caloduc apporte de la chaleur depuis l'extérieur aux cellules électrochimiques C qui utilisent dans ce cas du chlorure double de sodium et d'aluminium (NaAICU) comme électrolyte et qui nécessitent des températures de fonctionnement élevées, typiquement entre 300°C et 400°C. Autrement dit, le caloduc 200 divulgué a uniquement pour fonction de chauffer les cellules électrochimiques et n'est pas prévu pour évacuer la chaleur interne à l'emballage. Du potassium est utilisé comme fluide caloporteur, et ce potassium se condense au niveau de la zone refroidie 230. Ainsi, FR 2 539 919 ne divulgue en aucun cas un système de refroidissement des cellules électrochimiques. Rien dans cette demande ne concerne la gestion thermique d'un accumulateur au lithium qui diffère de celle d'un accumulateur au NaAICLt puisqu'il faut lui apporter de la chaleur et non pas le refroidir en fonctionnement. The patent application FR 2,539,919 describes a battery 100, reproduced in FIG. 1B, comprising a plurality of electrochemical cells C arranged inside a thermal protection envelope 300 and a heat pipe 200. The heated zone 240 of the heat pipe located inside the casing 300 while being heated by a catalytic converter. However, in the disclosed configuration, the heat pipe brings heat from outside to the electrochemical cells C which in this case use double chloride of sodium and aluminum (NaAICU) as the electrolyte and which require high operating temperatures, typically between 300 ° C and 400 ° C. In other words, the disclosed heat pipe 200 only serves to heat the electrochemical cells and is not intended to evacuate the heat inside the package. Potassium is used as heat transfer fluid, and this potassium condenses at the cooled zone 230. Thus, FR 2 539 919 does not disclose in any case a cooling system of the electrochemical cells. Nothing in this application relates to the thermal management of a lithium battery which differs from that of a NaAICLt accumulator since it must be provided with heat and not cool in operation.
II existe ainsi un besoin d'amélioration des accumulateurs et des batteries au lithium, notamment afin d'assurer à la fois une meilleure protection thermique et mécanique de la (des) cellule(s) électrochimique(s) et une gestion thermique la plus efficace possible de cette (ces) dernière(s), même en cas de chaleur excessive à l'intérieur et/ou à l'extérieur de l'emballage qui la(les) loge.  There is thus a need for improvement of batteries and lithium batteries, in particular to ensure both better thermal and mechanical protection of the electrochemical cell (s) and the most efficient thermal management possible of this (these) last (s), even in case of excessive heat inside and / or outside of the packaging which (the) lodge (s).
Le but de l'invention est de répondre au moins en partie à ce besoin.  The object of the invention is to respond at least in part to this need.
Exposé de l'invention  Presentation of the invention
Pour ce faire, l'invention a pour objet sous un de ses aspects un accumulateur électrochimique au lithium comportant au moins un premier emballage logeant au moins une cellule électrochimique, ledit premier emballage comportant au moins:  To do this, the subject of the invention is, in one of its aspects, an electrochemical lithium battery comprising at least a first package housing at least one electrochemical cell, said first package comprising at least:
- une couche interne, isolante thermiquement, adaptée pour confiner à l'intérieur d'un premier emballage la chaleur dégagée même en cas de fonctionnement anormal d'une cellule C et pour protéger la (les) cellule(s) de la chaleur externe au premier emballage,  an inner layer, thermally insulating, adapted to confine inside the first packaging the heat released even in the event of abnormal operation of a cell C and to protect the cell (s) from the external heat at first packaging,
- une couche externe superposée sur la couche interne, la couche externe étant résistante mécaniquement et résistante au feu, et  an outer layer superimposed on the inner layer, the outer layer being mechanically resistant and fire-resistant, and
- un dispositif de refroidissement comportant au moins un caloduc dont l'enceinte traverse le(s) premier(s) emballage(s) de manière étanche et de telle sorte que la zone chauffée du(des) caloduc(s) est située à l'intérieur du(des) premier(s) emballage(s) et que la zone refroidie du(des) caloduc(s) est située à l'extérieur du(des) premier(s) emballage(s).  a cooling device comprising at least one heat pipe whose enclosure passes through the first package (s) in a sealed manner and that the heated zone of the heat pipe (s) is located at inside the first package (s) and that the cooled area of the heat pipe (s) is located outside the first package (s).
Par « zone chauffée d'un caloduc », au sens de l'invention, on désigne le sens usuel technologique, à savoir la zone du caloduc où le liquide caloporteur du caloduc reçoit de la chaleur et s'évapore. La zone chauffée est encore usuellement appelée évaporateur. Par « zone refroidie d'un caloduc », au sens de l'invention, on désigne également le sens usuel technologique, à savoir la zone du caloduc où le liquide caloporteur du caloduc transmet de la chaleur et se condense. La zone refroidie est encore usuellement appelée condenseur. Pour plus de détails, on pourra se reporter notamment à la publication [1]. For the purposes of the invention, the term "heated zone of a heat pipe" denotes the usual technological meaning, namely the zone of the heat pipe where the heat transfer fluid of the heat pipe receives heat and evaporates. The heated zone is still usually called an evaporator. For the purposes of the invention, the term "cooled zone of a heat pipe" also refers to the usual technological meaning, namely the zone of the heat pipe where the heat transfer fluid of the heat pipe transmits heat and condenses. The cooled zone is still usually called a condenser. For more details, refer to the publication [1].
L'accumulateur selon l'invention peut loger une ou plusieurs cellules électrochimiques dans un premier emballage. Un emballage selon l'invention remplit deux fonctions : une fonction de protection mécanique et de résistance au feu, et une fonction d'isolation thermique. L'isolation thermique doit être suffisante pour permettre à la (aux) cellules électrochimique(s) d'être protégées de chaleurs extrêmes à l'extérieur, qui peuvent être notamment causées par le fonctionnement anormal d'une cellule électrochimique voisine à l'extérieur.  The accumulator according to the invention can house one or more electrochemical cells in a first package. A package according to the invention fulfills two functions: a function of mechanical protection and fire resistance, and a thermal insulation function. The thermal insulation must be sufficient to allow the electrochemical cell (s) to be protected from extreme heat outside, which can be caused in particular by the abnormal operation of a neighboring electrochemical cell outside. .
Par « fonctionnement anormal », on désigne une élévation de la température et de la pression au-delà de celle prévue en fonctionnement normal, qui est suffisamment grande pour causer une dégradation de la cellule en cause et/ou un emballement thermique de la (des) cellule(s) alentour.  "Abnormal operation" means an increase in temperature and pressure beyond that expected in normal operation, which is large enough to cause degradation of the cell and / or thermal runaway of the ) cell (s) around.
Ainsi, le dispositif de refroidissement est adapté pour évacuer la chaleur confinée par la couche interne à l'intérieur de l'accumulateur même en cas de fonctionnement anormal de la cellule électrochimique.  Thus, the cooling device is adapted to evacuate the heat confined by the inner layer inside the accumulator even in case of abnormal operation of the electrochemical cell.
La gestion thermique de l'accumulateur en fonctionnement normal ou anormal est en conséquence assurée par le dispositif de refroidissement.  Thermal management of the accumulator in normal or abnormal operation is therefore ensured by the cooling device.
Typiquement, un caloduc mis en œuvre dans l'invention comprend les éléments suivants :  Typically, a heat pipe implemented in the invention comprises the following elements:
- une enveloppe tabulaire en aluminium, acier (doux, inoxydable, ...), cuivre, ... - a tabular envelope made of aluminum, steel (soft, stainless, ...), copper, ...
- un fluide diphasique à l'intérieur de l'enveloppe tubulaire, à la température d'utilisation, comme par exemple l'eau, l'ammoniac, le méthanol, Péthanol, l'acétone, le toluène, l'heptane, ... a diphasic fluid inside the tubular casing, at the temperature of use, such as, for example, water, ammonia, methanol, ethanol, acetone, toluene, heptane, .
- le cas échéant, un milieu poreux capillaire comme une toile ou une poudre métallique frittée, ou des rainures à l'intérieur de l'enveloppe tubulaire.  where appropriate, a porous capillary medium such as a sintered metal cloth or powder, or grooves inside the tubular envelope.
On veille à ce que l'association du fluide diphasique et du matériau d'enveloppe respecte les contraintes liées principalement à la corrosion.  It is ensured that the combination of the two-phase fluid and the shell material respects the constraints mainly related to corrosion.
Avantageusement, le diamètre du caloduc selon l'invention est de l'ordre de quelques millimètres, de préférence compris entre 1 mm et 2 cm, de préférence encore entre 2 et 6 mm. La longueur du caloduc peut être quelconque, puisqu'elle n'affecte que très peu l'évacuation thermique. Par exemple, le caloduc peut dépasser de l'emballage de 1 mm à 2 cm. Advantageously, the diameter of the heat pipe according to the invention is of the order of a few millimeters, preferably between 1 mm and 2 cm, more preferably between 2 mm and 2 cm. and 6 mm. The length of the heat pipe can be arbitrary, since it affects only very little thermal evacuation. For example, the heat pipe may protrude from the package of 1 mm to 2 cm.
Selon une variante avantageuse, la conductivité thermique K de la couche interne est inférieure à 0,05W.m" ^K"1. Une conductivité thermique très faible de la couche interne permet de confiner avec une grande efficacité la chaleur interne à l'emballage selon l'invention, en cas de fonctionnement anormal d'une cellule électrochimique ou de la protéger de la chaleur externe à l'emballage. According to an advantageous variant, the thermal conductivity K of the inner layer is less than 0,05W.m "^ K" 1. A very low thermal conductivity of the inner layer makes it possible to confine with great efficiency the internal heat of the packaging according to the invention, in the event of abnormal operation of an electrochemical cell or to protect it from heat external to the packaging. .
Selon une autre variante avantageuse, la couche externe apporte une résistance au feu selon la norme SAE J2464.  According to another advantageous variant, the outer layer provides fire resistance according to the SAE J2464 standard.
Selon une autre variante avantageuse, le module d'Young E de la couche externe de protection est supérieur à lGPa.  According to another advantageous variant, the Young's modulus E of the outer protective layer is greater than 1GPa.
Selon un mode de réalisation avantageux, la zone refroidie du caloduc est située au-dessus du premier emballage, le caloduc constituant ainsi un thermosiphon ou caloduc assisté par gravité. On précise que dans le cadre de l'invention, on entend par « thermosiphon diphasique », le sens usuel connu de l'homme du métier tel que défini dans la publication [1]. Ainsi, un thermosiphon diphasique est un caloduc qui permet de transférer de la chaleur par évaporation/condensation d'un fluide à l'intérieur d'une enveloppe sans aucune structure capillaire, c'est-à-dire avec un retour des condensais par gravité à l'intérieur de l'enveloppe.  According to an advantageous embodiment, the cooled zone of the heat pipe is located above the first package, the heat pipe thus constituting a thermosiphon or heat pipe assisted by gravity. It is specified that in the context of the invention, the term "diphasic thermosiphon", the usual meaning known to those skilled in the art as defined in the publication [1]. Thus, a diphasic thermosiphon is a heat pipe that transfers heat by evaporation / condensation of a fluid inside an envelope without any capillary structure, that is to say with a gravity return of gravity inside the envelope.
Un caloduc assisté par la gravité [1] est un caloduc dans lequel il existe une structure capillaire, généralement des rainures, mais le retour des condensais du condenseur à l'évaporateur est assuré par la gravité, l'évaporateur du caloduc étant à une position plus basse que le condenseur. La structure capillaire n'a donc pas pour but de ramener les condensais; mais d'améliorer les coefficients d'échange en évaporation et en condensation, et de repousser la limite d'entraînement.  A gravity-assisted heat pipe [1] is a heat pipe in which there is a capillary structure, usually grooves, but the return of condensates from the condenser to the evaporator is ensured by the gravity, the evaporator of the heat pipe being at a position lower than the condenser. The capillary structure is therefore not intended to reduce the condensates; but to improve the exchange coefficients in evaporation and condensation, and to push back the training limit.
Selon une variante avantageuse de l'invention, au moins un caloduc constitue une borne de sortie de courant de l'accumulateur. Cela permet avantageusement de s'affranchir d'une étape de soudure d'une borne de sortie sur une partie de l'accumulateur, comme dans les accumulateurs selon l'état de l'art.  According to an advantageous variant of the invention, at least one heat pipe constitutes a current output terminal of the accumulator. This advantageously makes it possible to dispense with a welding step of an output terminal on a part of the accumulator, as in the accumulators according to the state of the art.
Selon un mode de réalisation, le(les) caloduc(s) est (sont) adapté(s) pour limiter voire supprimer la phase liquide au sein de son (leur) enceinte en cas de fonctionnement anormal de la (des) cellule(s) électrochimique(s) dont il(s) reçoit (vent) la chaleur au niveau de sa (leur) zone chauffée. Un caloduc configuré d'une telle manière présente un phénomène de saturation comme illustré en figure 2: lorsque la température devient trop importante, le caloduc est dimensionné de telle sorte que la phase liquide s'évapore totalement. According to one embodiment, the (the) heat pipe (s) is (are) adapted (s) to limit or even eliminate the liquid phase within its (their) enclosure in case of abnormal operation of the cell (s) (s) ) electrochemical (s) from which it (s) receives (wind) heat at its (their) heated zone. A heat pipe configured in such a manner has a saturation phenomenon as illustrated in FIG. 2: when the temperature becomes too great, the heat pipe is dimensioned so that the liquid phase evaporates completely.
Ainsi, la quantité de chaleur transmise par la zone chauffée à la zone refroidie du caloduc atteint un maximum qui ne croît plus de manière significative au-delà de la température de saturation, qui est choisie comme étant la température de fonctionnement anormal d'une cellule électrochimique. La chaleur excessive est ainsi totalement confinée par l'emballage et par le caloduc.  Thus, the amount of heat transmitted by the heated zone to the cooled zone of the heat pipe reaches a maximum that does not increase significantly beyond the saturation temperature, which is chosen as the abnormal operating temperature of a cell. electrochemical. Excessive heat is thus completely confined by the packaging and the heat pipe.
Selon une variante de réalisation de la couche interne, celle-ci comprend une matrice en polymère thermodurcissable ou thermoplastique, cette matrice étant majoritairement chargée en aérogel de silice ou autre charge particulaire.  According to an alternative embodiment of the inner layer, the latter comprises a thermosetting or thermoplastic polymer matrix, this matrix being mainly loaded with silica airgel or other particulate filler.
Le matériau constituant la matrice de la couche interne est choisi de préférence parmi l'uréthane, l'acrylate, le méthacrylate, le polyéther et la silicone, ou est un polymère vinylique notamment styrènique, un polymère polyoléfïne réticulé ou non, un polymère de type polyester insaturé ou une résine époxy.  The material constituting the matrix of the inner layer is preferably chosen from urethane, acrylate, methacrylate, polyether and silicone, or is a vinylic polymer, in particular styrene, a polyolefin polymer which may or may not be crosslinked, a polymer of the type unsaturated polyester or an epoxy resin.
Selon une variante de la couche externe de protection, celle-ci comprend une matrice thermodurcissable dans laquelle est noyé un renfort fibreux.  According to a variant of the outer protective layer, the latter comprises a thermosetting matrix in which is embedded a fibrous reinforcement.
Le matériau constituant la matrice de la couche externe peut être avantageusement choisi parmi l'uréthane, l'acrylate, le méthacrylate, ou étant un polymère vinylique notamment styrènique, un polymère de type polyester insaturé ou une résine époxy.  The material constituting the matrix of the outer layer may advantageously be chosen from urethane, acrylate or methacrylate, or it may be a vinylic polymer, especially styrene, an unsaturated polyester polymer or an epoxy resin.
Le matériau constituant le renfort fibreux peut avantageusement être à fibres courtes ou longues, de préférence des fibres de verre, du carbone, un polyamide aromatique, du carbure de silicium SiC, des fibres de bambou, du lin, des fibres de coco ou de chanvre.  The material constituting the fibrous reinforcement may advantageously be short or long fibers, preferably glass fibers, carbon, an aromatic polyamide, silicon carbide SiC, bamboo fibers, flax, coconut fibers or hemp fibers. .
L'(les) enceinte(s) du (des) caloduc(s) peu(ven)t être de section circulaire ou prismatique. Un caloduc avec une telle section d'enceinte peut éventuellement être adapté pour servir ainsi de mandrin d'enroulement d'une cellule.  The enclosure (s) of the heat pipe (s) may be of circular or prismatic section. A heat pipe with such a chamber section may optionally be adapted to serve as a winding mandrel of a cell.
Selon un mode de réalisation préféré, la cellule électrochimique C est sous la forme d'une bobine enroulée autour de l'enceinte du caloduc.  According to a preferred embodiment, the electrochemical cell C is in the form of a coil wound around the enclosure of the heat pipe.
Selon un autre mode de réalisation, l'enceinte d'au moins un caloduc est agencée en périphérie de la (des) cellules électrochimique(s) C dans un interstice à l'intérieur du premier emballage.  According to another embodiment, the enclosure of at least one heat pipe is arranged on the periphery of the electrochemical cell (s) C in a gap inside the first package.
Selon un premier mode de réalisation, l'accumulateur électrochimique comporte une pluralité d'un nombre de n premiers emballages, dont un nombre égal à n-1 des premiers emballages loge chacun une cellule électrochimique, les (n-1) premiers emballages étant eux- mêmes logés à l'intérieur de l'autre premier emballage. According to a first embodiment, the electrochemical accumulator comprises a plurality of a number of n first packages, of which a number equal to n-1 of the first Each package houses an electrochemical cell, the (n-1) first packages being themselves housed inside the other first package.
Selon un deuxième mode de réalisation, l'accumulateur comporte un deuxième emballage à base d'alliage métallique, tel qu'un alliage d'aluminium, logeant la(les) cellule(s) électrochimique(s), le deuxième emballage étant lui-même logé de manière étanche dans le premier emballage. On peut selon ce mode mettre en œuvre l'invention sur des accumulateurs à emballage en alliage métallique selon l'état de l'art.  According to a second embodiment, the accumulator comprises a second metal alloy package, such as an aluminum alloy, housing the electrochemical cell (s), the second package being itself even housed tightly in the first package. According to this embodiment, the invention can be applied to metal alloy packaging batteries according to the state of the art.
Selon ce deuxième mode, le premier emballage comporte, sur la couche interne, un revêtement électriquement conducteur. Le revêtement électriquement conducteur peut être de préférence à base de particules métalliques frittées par frittage photonique ou de graphites conducteurs, de préférence déposé sous forme de peinture ou d'aérosol. Son rôle est d'assurer la compatibilité électromagnétique de la batterie.  According to this second embodiment, the first package comprises, on the inner layer, an electrically conductive coating. The electrically conductive coating may preferably be based on photon sintered metal particles or conductive graphites, preferably deposited as a paint or aerosol. Its role is to ensure the electromagnetic compatibility of the battery.
Selon une variante mode de réalisation, le premier emballage comporte sur sa face interne, un revêtement à fonction de barrière, adapté pour assurer la neutralité chimique de la couche interne vis-à-vis de l'électrolyte de la cellule électrochimique C  According to an alternative embodiment, the first package has on its inner face, a coating with a barrier function, adapted to ensure the chemical neutrality of the inner layer vis-à-vis the electrolyte of the electrochemical cell C
Le matériau du revêtement barrière peut être choisi parmi le polypropylène, le polyéthylène, un polymère de la famille des polyaryléthercétones (PAEK), de préférence le polyétheréthercétone (PEEK™), ou un polymère de la famille des polyimides.  The material of the barrier coating may be chosen from polypropylene, polyethylene, a polymer of the polyaryletherketone (PAEK) family, preferably polyetheretherketone (PEEK ™), or a polymer of the polyimide family.
Description détaillée  detailed description
D'autres avantages et caractéristiques ressortiront mieux à la lecture de la description détaillée, faite à titre illustratif en référence aux figures suivantes parmi lesquelles :  Other advantages and features will emerge more clearly on reading the detailed description, given by way of illustration with reference to the following figures among which:
- la figure 1A représente un accumulateur lithium-ion avec un dispositif de refroidissement selon l'état de l'art,  FIG. 1A represents a lithium-ion accumulator with a cooling device according to the state of the art,
- la figure 1B représente un accumulateur au NaAICU selon l'état de l'art, FIG. 1B represents a NaAICU accumulator according to the state of the art,
- la figure 2 illustre le phénomène de saturation d'un caloduc, FIG. 2 illustrates the phenomenon of saturation of a heat pipe,
- la figure 3 illustre en vue schématique l'agencement relatif entre l'emballage dans lequel est logée une cellule électrochimique et un caloduc d'un accumulateur lithium- ion selon l'invention,  FIG. 3 schematically illustrates the relative arrangement between the package in which an electrochemical cell is housed and a heat pipe of a lithium-ion accumulator according to the invention,
- la figure 4 illustre un exemple de réalisation d'un accumulateur lithium-ion selon l'invention,  FIG. 4 illustrates an exemplary embodiment of a lithium-ion battery according to the invention,
- la figure 5 illustre un autre exemple de réalisation d'un accumulateur lithium- ion selon l'invention, - la figure 6 illustre encore un autre exemple de réalisation d'un accumulateur lithium-ion selon l'invention, FIG. 5 illustrates another exemplary embodiment of a lithium-ion battery according to the invention, FIG. 6 illustrates yet another embodiment of a lithium-ion battery according to the invention,
- la figure 7 illustre encore un autre exemple de réalisation d'un accumulateur lithium-ion selon l'invention.  - Figure 7 illustrates yet another embodiment of a lithium-ion battery according to the invention.
Les figures 1 A à 2 ont déjà été décrites en détail en préambule. Elles ne sont donc pas commentées ci-après. Figures 1A to 2 have already been described in detail in the preamble. They are therefore not commented on below.
Comme représenté en figure 3, l'accumulateur 1 selon l'invention comprend un emballage 3 qui loge au moins une cellule électrochimique au lithium.  As represented in FIG. 3, the accumulator 1 according to the invention comprises a package 3 which houses at least one lithium electrochemical cell.
L'emballage 3 comporte une couche externe 4 superposée sur une couche interne 5, isolante thermiquement.  The package 3 comprises an outer layer 4 superimposed on an inner layer 5, thermally insulating.
La couche externe 4 est résistante mécaniquement et apporte une résistance au feu. La couche externe 4 est de préférence en polymère de type résine époxy, résine polyuréthane, résine polyvynilique, résine polyester, le cas échéant avec des renforts de type fibres de verre ou fibres de carbone. L'épaisseur de la couche 4 est comprise de préférence entre 300 μιη et 2 mm, de préférence encore de l'ordre de 1 mm.  The outer layer 4 is mechanically resistant and provides fire resistance. The outer layer 4 is preferably epoxy resin polymer, polyurethane resin, polyvinyl resin, polyester resin, optionally with reinforcements of the glass fiber type or carbon fiber. The thickness of the layer 4 is preferably between 300 μιη and 2 mm, more preferably of the order of 1 mm.
La couche interne 5 est de préférence en polyéthylène (PE) ou en polypropylène (PP), ou en PTFE ou de PFE, avec éventuellement des charges isolantes thermiquement de type  The inner layer 5 is preferably made of polyethylene (PE) or of polypropylene (PP), or of PTFE or of PFE, with possibly thermally insulating fillers of the type
nano-argile ou alumine par exemple. L'épaisseur de la couche 5 est de préférence inférieure à 300 μιη de préférence et supérieure à 20 nano mètres (nm). nano-clay or alumina, for example. The thickness of the layer 5 is preferably less than 300 μιη preferably and greater than 20 nanometers (nm).
Un revêtement 6 recouvre la couche interne 5. Ce revêtement 6 peut avoir différentes fonctions comme expliqué ci-après.  A coating 6 covers the inner layer 5. This coating 6 may have different functions as explained below.
Le dispositif de refroidissement de l'accumulateur 1 comprend un caloduc 2 comportant une enceinte étanche 21, à l'intérieur de laquelle circule un fluide caloporteur 22. Ce fluide caloporteur est adapté pour fonctionner en régime linéaire à la température de fonctionnement d'une cellule électrochimique au lithium, et peut être typiquement de l'eau.  The cooling device of the accumulator 1 comprises a heat pipe 2 comprising a sealed enclosure 21, inside which circulates a coolant 22. This heat transfer fluid is adapted to operate in linear mode at the operating temperature of a cell electrochemical lithium, and can typically be water.
Le caloduc 2 traverse l'emballage 3 de manière étanche. La zone chauffée 24 est située au sein de l'emballage 3. La zone refroidie 23 est située à l'extérieur de l'emballage 3.  The heat pipe 2 passes through the package 3 in a sealed manner. The heated zone 24 is located within the package 3. The cooled zone 23 is located outside the package 3.
Typiquement, le diamètre du caloduc 2 est de l'ordre de quelques millimètres, de préférence compris entre 1 mm et 2 cm, de préférence encore entre 2 et 6 mm. La longueur du caloduc peut être quelconque, puisqu'elle n'affecte que très peu l'évacuation thermique. Par exemple, le caloduc peut dépasser de l'emballage de 1 mm à 2 cm. Typically, the diameter of the heat pipe 2 is of the order of a few millimeters, preferably between 1 mm and 2 cm, more preferably between 2 and 6 mm. The length of heat pipe can be any, since it affects very little thermal evacuation. For example, the heat pipe may protrude from the package of 1 mm to 2 cm.
Un exemple de réalisation de l'invention est représenté en figure 4. Dans cet exemple, une seule cellule électrochimique C est agencée à l'intérieur du premier emballage 3. La cellule électrochimique est sous la forme d'une bobine enroulée autour du caloduc 2. L'enceinte 21 du caloduc 2 a une section circulaire. Les bornes positive 7 et négative 8 traversent également l'emballage 3 de manière étanche. Selon une variante, il est possible d'utiliser le caloduc lui-même en tant que borne de sortie du courant de l'accumulateur.  An exemplary embodiment of the invention is shown in FIG. 4. In this example, a single electrochemical cell C is arranged inside the first package 3. The electrochemical cell is in the form of a coil wound around the heat pipe 2 The enclosure 21 of the heat pipe 2 has a circular section. The positive 7 and negative 8 terminals also pass through the package 3 sealingly. According to one variant, it is possible to use the heat pipe itself as the output terminal of the current of the accumulator.
Le revêtement 6 quant à lui assure la neutralité de la couche interne 5 vis-à-vis de l'électrolyte de la cellule électrochimique C.  The coating 6 ensures the neutrality of the inner layer 5 vis-à-vis the electrolyte of the electrochemical cell C.
Le premier emballage 3 étant très isolant thermiquement, avec une conductivité thermique de la couche interne 5 inférieure à 0,05 W.m^.K"1, la gestion thermique en fonctionnement normal de la cellule 6 est assurée par le caloduc 2. The first package 3 being very thermally insulating, with a thermal conductivity of the inner layer less than 0.05 Wm ^ .K "1 , the thermal management in normal operation of the cell 6 is provided by the heat pipe 2.
La zone chauffée 24 se trouve à l'intérieur du cylindre creux formé par la cellule C enroulée sur elle-même, et en contact thermique avec celle-ci. Ainsi, une grande quantité de chaleur est transmise de la cellule C à la zone chauffée 24. Le fluide caloporteur 22 suit alors un cycle d'évaporation et de condensation : il s'évapore au niveau de la zone chauffée 24, et se condense au niveau de la zone refroidie 23. Cette zone refroidie 23 peut éventuellement comporter un diffuseur thermique afin d'évacuer la chaleur transmise lors de la condensation du fluide 22.  The heated zone 24 is inside the hollow cylinder formed by the cell C wound on itself, and in thermal contact therewith. Thus, a large amount of heat is transmitted from the cell C to the heated zone 24. The heat transfer fluid 22 then follows an evaporation and condensation cycle: it evaporates at the heated zone 24, and condenses at the level of the cooled zone 23. This cooled zone 23 may optionally comprise a thermal diffuser in order to evacuate the heat transmitted during the condensation of the fluid 22.
Dans cet exemple, la zone chauffée 24 étant située en dessous la zone 23, le caloduc 2 constitue un thermosiphon et fonctionne grâce à la gravité : le fluide condensé retombe par gravité vers la zone chauffée 23 où il entreprend un nouveau cycle d'évaporation et de condensation.  In this example, the heated zone 24 being located below the zone 23, the heat pipe 2 constitutes a thermosiphon and operates thanks to gravity: the condensed fluid falls by gravity to the heated zone 23 where it undertakes a new evaporation cycle and condensation.
En cas de fonctionnement anormal de la cellule C, la couche interne 5 confine la chaleur à l'intérieur de l'emballage 3. De plus, un caloduc présente une limite de saturation comme représenté en figure 5. Au-delà d'une certaine température, il cesse de transmettre la chaleur. Ainsi, en cas de fonctionnement anormal de la cellule C, la chaleur n'est pas non plus transmise par le caloduc 2. La chaleur est ainsi efficacement confinée à l'intérieur de l'emballage 3 selon l'invention.  In case of abnormal operation of the cell C, the inner layer 5 confines the heat inside the package 3. In addition, a heat pipe has a saturation limit as shown in FIG. 5. Beyond a certain temperature, it stops transmitting heat. Thus, in the event of abnormal operation of the cell C, the heat is also not transmitted by the heat pipe 2. The heat is thus effectively confined within the package 3 according to the invention.
D'autre part, en cas de température extérieure à l'emballage 3 élevée, la couche interne 5 empêche la dégradation de la cellule électrochimique C ou autrement dit, protège l'accumulateur électrochimique 1. L'accumulateur illustré en figure 3 est réalisé en enroulant autour de l'enceinte du caloduc 2 la cellule électrochimique C. L'enceinte 21 du caloduc 2 est ainsi adaptée pour servir de mandrin lors de la fabrication de la cellule. On the other hand, in case of temperature outside the high packaging 3, the inner layer 5 prevents degradation of the electrochemical cell C or in other words, protects the electrochemical accumulator 1. The accumulator illustrated in FIG. 3 is made by winding around the enclosure of the heat pipe 2 the electrochemical cell C. The enclosure 21 of the heat pipe 2 is thus adapted to serve as a mandrel during the manufacture of the cell.
Pour réaliser les différentes couches 4, 5 de l'emballage, on peut envisager différents procédés de fabrication. Un procédé par injection peut être ainsi avantageux pour la réalisation de la couche d'isolation thermique 5, à partir d'un polymère thermoplastique et d'une charge faible K.  To achieve the different layers 4, 5 of the package, one can consider different manufacturing processes. An injection method can thus be advantageous for producing the thermal insulation layer 5, from a thermoplastic polymer and a low load K.
Les procédés classiques de mise en œuvre des composites comme l'injection réactive, les différentes techniques d'injection connues sous la dénomination « Sheet Molding Compound » (SMC), « Bulk Molding Compound » (BMC), « Resin Transfer Molding » (RTM), le moulage au contact peuvent être utilisés pour la mise en œuvre de la couche externe 4 en polymère thermodurcissable.  Conventional processes for the use of composites such as reactive injection, the various injection techniques known under the name "Sheet Molding Compound" (SMC), "Bulk Molding Compound" (BMC), "Resin Transfer Molding" (RTM) ), the contact molding can be used for the implementation of the outer layer 4 of thermosetting polymer.
Un procédé d'injection bi-matière thermoplastique-thermodurcissable est envisageable pour la réalisation en une seule étape des deux couches 4, 5 l'emballage. De manière avantageuse, les bornes positives 7 et négatives 8 peuvent être déjà présentes au début du procédé d'injection. On peut envisager de réaliser les couches 4, 5 par le procédé d'injection décrit et revendiqué dans la demande de brevet FR 14 51546 au nom de la demanderesse.  A thermoplastic-thermosetting bi-material injection process can be envisaged for producing the two layers 4, 5, in a single step. Advantageously, the positive 7 and negative 8 terminals may already be present at the beginning of the injection process. It is conceivable to produce the layers 4, 5 by the injection method described and claimed in the patent application FR 14 51546 in the name of the applicant.
On décrit maintenant un exemple de réalisation des couches 4, 5 d'emballage avec une matrice à renfort fibreux.  An embodiment of the packaging layers 4, 5 with a fibrous reinforcement matrix is now described.
Cet exemple consiste en la création de deux demi-coques qui seront rassemblées autour de la cellule électrochimique C. L'introduction de l'électrolyte est faite au moment du rassemblement des deux demi-coques par injection avant soudure plastique/collage final.  This example consists in the creation of two half-shells which will be gathered around the electrochemical cell C. The introduction of the electrolyte is made at the time of the gathering of the two half-shells by injection before plastic welding / final bonding.
Cet exemple avec des matrices à renfort fibreux peut être réalisé selon une technologie RTM, couplée à une injection thermoplastique avec charge. On réalise ainsi les étapes successives suivantes :  This example with fibrous reinforcement matrices can be realized according to a RTM technology, coupled to a thermoplastic injection with charge. The following successive steps are thus carried out:
1- introduction des différentes épaisseurs du tissu de fibres de verre avec les bornes de connexion 7, 8 dans un moule RTM, préalablement chauffé,  1-introduction of the different thicknesses of the glass fiber fabric with the connection terminals 7, 8 into a previously heated RTM mold,
2- fermeture du moule et mise sous vide du moule,  2- closing of the mold and evacuation of the mold,
3- injection des précurseurs de la résine époxyde dans le moule, ce qui conduit à l'imprégnation des fibres,  3- injection of the precursors of the epoxy resin into the mold, which leads to the impregnation of the fibers,
4- cuisson de la résine époxyde suivant le temps préconisé à la température préconisée, 5- réglage de la température du moule pour l'injection de matière thermoplastique,4- baking the epoxy resin according to the recommended time at the recommended temperature, 5- adjustment of the mold temperature for the injection of thermoplastic material,
6- ouverture du clapet dans le moule pour définir la zone de moulage du renfort thermique de la cellule électrochimique, Opening of the valve in the mold to define the molding zone of the thermal reinforcement of the electrochemical cell,
7- injection de polyéthylène (PE) fortement chargé avec des particules de taille micronique, de matériaux d'isolant thermique,  7- injection of highly filled polyethylene (PE) with micron-sized particles, thermal insulation materials,
8- extraction du moule de l'objet formé et détourage/décarottage des excès matières,  8- extraction of the mold from the formed object and trimming / unraveling of excess materials,
9- rassemblement des deux demi-coques formées autour de la cellule électrochimique C bobinée autour de son caloduc 2 et soudure thermoplastique autour d'une double aiguille, par mise sous vide avec l'une des aiguilles et injection simultanée de l'électrolyte par l'autre des aiguilles,  9- gathering of the two half-shells formed around the electrochemical cell C wound around its heat pipe 2 and thermoplastic welding around a double needle, by evacuation with one of the needles and simultaneous injection of the electrolyte by the other needles,
10- retrait des aiguilles tout en complétant la soudure thermoplastique, 10- removal of the needles while completing the thermoplastic welding,
11- collage de matière thermodurcissable des zones thermodurcissables afin d'assurer une homogénéité de renfort pour la tenue au feu et de renfort mécanique. 11- bonding of thermosetting material thermosetting areas to ensure homogeneity of reinforcement for fire resistance and mechanical reinforcement.
Un autre exemple de réalisation de l'invention est illustré en figure 5. Selon cet exemple, l'accumulateur 1 comprend une pluralité de cellules électrochimiques C. Chaque cellule électrochimique est agencée de manière étanche au sein d'un emballage 3' selon l'état de l'art. Cet emballage 3' est de type à alliage métallique, tel qu'en alliage d'aluminium, ou plastique. Cet emballage 3' selon l'état de l'art est logé de manière étanche dans l'emballage 3 selon l'invention. Plusieurs caloducs 2 traversent de manière étanche l'emballage 3 et ont une de leurs extrémités agencée dans des interstices 9 au sein de l'emballage 3. Leurs zones chauffées 24 se trouvent ainsi au contact des emballages 3' selon l'état de l'art, qui sont conducteurs thermiquement et donc qui diffusent la chaleur libérée par les cellules électrochimiques C. Le contact thermique entre une zone chauffée 24 de caloduc et l'emballage 3' d'une cellule électrochimique peut être amélioré en interposant de la graisse conductrice thermiquement.  Another exemplary embodiment of the invention is illustrated in FIG. 5. According to this example, the accumulator 1 comprises a plurality of electrochemical cells C. Each electrochemical cell is arranged in a sealed manner within a package 3 'according to FIG. state of the art. This 3 'package is metal alloy type, such as aluminum alloy, or plastic. This packaging 3 'according to the state of the art is housed in a sealed manner in the package 3 according to the invention. Several heat pipes 2 pass tightly through the package 3 and have one of their ends arranged in interstices 9 within the package 3. Their heated zones 24 are thus in contact with the packages 3 'according to the state of the package. art, which are thermally conductive and thus which diffuse the heat released by the electrochemical cells C. The thermal contact between a heated zone 24 of heat pipe and the 3 'packaging of an electrochemical cell can be improved by interposing thermally conductive grease .
De préférence, dans cet exemple, un revêtement 6 électriquement conducteur recouvre l'intérieur de la couche interne 5 de l'emballage 3, afin d'assurer la compatibilité électromagnétique de la batterie.  Preferably, in this example, an electrically conductive coating 6 covers the inside of the inner layer 5 of the package 3, in order to ensure the electromagnetic compatibility of the battery.
En cas de fonctionnement anormal d'une cellule C, la couche interne 5 confine la chaleur à l'intérieur de l'emballage 3. De même, en cas de chaleur extérieur à l'emballage 3 élevée, la couche interne 5 empêche la dégradation des cellules électrochimiques C et ainsi protège l'accumulateur électrochimique 1. D'autres variantes et améliorations peuvent être envisagées sans pour autant sortir du cadre de l'invention. In case of abnormal operation of a cell C, the inner layer 5 confines the heat inside the package 3. Similarly, in case of heat outside the high packaging 3, the inner layer 5 prevents degradation electrochemical cells C and thus protects the electrochemical accumulator 1. Other variants and improvements may be envisaged without departing from the scope of the invention.
Par exemple, on peut envisager un mode de réalisation d'un accumulateur avec plusieurs cellules électrochimiques C baignant dans un même électrolyte dans l'emballage 3 selon l'invention. Un tel mode est illustré en figure 6 où l'on voit trois cellules agencées en parallèle dans un même emballage 3, avec un seul caloduc 2 de type puisé dont les zones chauffées 24 sont à l'intérieur et ses zones refroidies 23 à l'extérieur. Ce mode de réalisation est particulièrement avantageux lorsqu'on souhaite réaliser des cellules C de très grosse capacité.  For example, it is possible to envisage an embodiment of an accumulator with several electrochemical cells C immersed in the same electrolyte in the package 3 according to the invention. Such a mode is illustrated in FIG. 6, in which three cells arranged in parallel in the same package 3 are seen, with a single heat pipe 2 of pulsed type, the heated zones 24 of which are inside and its cooled zones 23 at the same time. outside. This embodiment is particularly advantageous when it is desired to produce C cells of very large capacity.
On peut aussi envisager un mode à « double emballage » selon lequel l'accumulateur électrochimique comporte une pluralité d'un nombre de n premiers emballages, dont un nombre égal à n-1 des premiers emballages loge chacun une cellule électrochimique C, les (n-1) premiers emballages étant eux-mêmes logés à l'intérieur de l'autre premier emballage. Ce mode est illustré en figure 7, où l'on voit deux cellules agencées en parallèle et chacun à l'intérieur d'un emballage 3 selon l'invention, un caloduc central 2 étant agencé entre ces deux emballages 3 eux-mêmes logés dans un troisième emballage 3 périphérique. It is also possible to envisage a "double packaging" mode according to which the electrochemical accumulator comprises a plurality of a number of n first packagings, of which a number equal to n-1 of the first packs each houses an electrochemical cell C, the (n -1) first packs being themselves housed inside the other first packaging. This mode is illustrated in FIG. 7, in which we see two cells arranged in parallel and each inside a package 3 according to the invention, a central heat pipe 2 being arranged between these two packages 3 themselves housed in a third peripheral package 3.
REFERENCE CITEE REFERENCE CITEE
[1] : Bonjour J, Lefevre F, Sartre V, Bertin Y, Romestant C, Ayel V et Platel V, « Systèmes Diphasiques De Contrôle Thermique - Thermosiphons Et Caloducs », Techniques de l'ingénieur, Vol. BE9545, 2011.  [1]: Hello J, Lefevre F, Sartre V, Bertin Y, Romantant C, Ayel V and Platel V, "Diphasic Systems of Thermal Control - Thermosyphons and Heatpipes", Engineering Techniques, Vol. BE9545, 2011.

Claims

REVENDICATIONS
1. Accumulateur électrochimique au lithium (1), comportant :  1. Lithium electrochemical accumulator (1), comprising:
• - au moins un premier emballage (3) logeant au moins une cellule électrochimique, ledit premier emballage (3) comportant au moins une couche interne (5), isolante thermiquement, adaptée pour confiner à l'intérieur du premier emballage la chaleur dégagée même en cas de fonctionnement anormal d'une cellule C et pour protéger la (les) cellule(s) de la chaleur externe au premier emballage (3) ,  At least one first package (3) housing at least one electrochemical cell, said first package (3) comprising at least one inner layer (5), thermally insulating, adapted to confine inside the first package the heat released even in case of abnormal operation of a cell C and to protect the cell (s) from external heat to the first package (3),
• une couche externe (4), superposée sur la couche interne (5), la couche externe étant résistante mécaniquement et résistante au feu,  An outer layer (4) superimposed on the inner layer (5), the outer layer being mechanically resistant and fire-resistant,
et  and
- un dispositif de refroidissement comportant au moins un caloduc (2) dont l'enceinte (21) traverse le(s) premier(s) emballage(s) (3) de manière étanche et de telle sorte que la zone chauffée (24) du caloduc est située à l'intérieur du(des) premier(s) emballage(s) (3) et que la zone refroidie (23) du caloduc est située à l'extérieur du(des) premier(s) emballage(s) (3).  - a cooling device comprising at least one heat pipe (2) whose enclosure (21) passes through the first package (s) (3) in a sealed manner and so that the heated zone (24) the heat pipe is located inside the first package (3) and that the cooled zone (23) of the heat pipe is located outside the first package (s) ) (3).
2. Accumulateur électrochimique selon la revendication 1, la conductivité thermique K de la couche interne (5) étant inférieure à 0,05W.m" ^K"1. 2. Electrochemical battery according to claim 1, the thermal conductivity K of the inner layer (5) being less than 0,05W.m "^ K" 1.
3. Accumulateur électrochimique selon l'une des revendications précédentes, le module d'Young E de la couche externe (4) étant supérieur à lGPa.  3. Electrochemical accumulator according to one of the preceding claims, the Young's modulus E of the outer layer (4) being greater than 1GPa.
4. Accumulateur électrochimique selon l'une des revendications précédentes, la zone refroidie (23) du caloduc étant située au-dessus du premier emballage (3), le caloduc (2) constituant ainsi un thermosiphon ou caloduc assisté par gravité.  4. electrochemical accumulator according to one of the preceding claims, the cooled zone (23) of the heat pipe being located above the first package (3), the heat pipe (2) thus constituting a thermosiphon or heat pipe assisted by gravity.
5. Accumulateur électrochimique selon l'une des revendications précédentes, au moins un caloduc (2) constituant une borne de sortie du courant de l'accumulateur.  5. electrochemical accumulator according to one of the preceding claims, at least one heat pipe (2) constituting an output terminal of the current of the accumulator.
6. Accumulateur électrochimique selon l'une des revendications précédentes, le(s) caloduc(s) étant adapté(s) pour limiter voire supprimer la phase liquide au sein de son (leur) enceinte en cas de fonctionnement anormal de la (des) cellule(s) électrochimique(s).  6. electrochemical accumulator according to one of the preceding claims, the (s) heat pipe (s) being adapted (s) to limit or eliminate the liquid phase within his (their) enclosure in case of abnormal operation of (the) electrochemical cell (s).
7. Accumulateur électrochimique selon l'une des revendications précédentes, la couche interne (5) comprenant une matrice en polymère thermodurcissable ou thermoplastique, cette matrice étant majoritairement chargée en aérogel de silice ou autre charge particulaire.  7. Electrochemical accumulator according to one of the preceding claims, the inner layer (5) comprising a matrix of thermosetting or thermoplastic polymer, this matrix being mainly loaded with airgel silica or other particulate filler.
8. Accumulateur électro chimique selon la revendication 7, le matériau constituant la matrice de la couche interne (5) étant choisi parmi l'uréthane, Pacrylate, le méthacrylate, le polyéther et la silicone, ou étant un polymère vinylique notamment styrènique, un polymère polyoléfme réticulé ou non, un polymère de type polyester insaturé ou une résine époxy. 8. electro-chemical accumulator according to claim 7, the material constituting the matrix of the inner layer (5) being chosen from urethane, acrylate, methacrylate, polyether and silicone, or being a vinyl polymer including styrene, a polyolefin polymer crosslinked or not, an unsaturated polyester type polymer or an epoxy resin.
9. Accumulateur électrochimique selon l'une des revendications précédentes, la couche externe (4) comprenant une matrice thermodurcissable dans laquelle est noyé un renfort fibreux.  9. electrochemical accumulator according to one of the preceding claims, the outer layer (4) comprising a thermosetting matrix in which is embedded a fibrous reinforcement.
10. Accumulateur électrochimique selon la revendication 9, le matériau constituant la matrice de la couche externe étant choisi parmi l'uréthane, l'acrylate, le méthacrylate, ou étant un polymère vinylique notamment styrènique, un polymère de type polyester insaturé ou une résine époxy.  10. electrochemical accumulator according to claim 9, the material constituting the matrix of the outer layer being selected from urethane, acrylate, methacrylate, or being a vinyl polymer including styrenic, unsaturated polyester polymer or an epoxy resin .
11. Accumulateur électrochimique selon la revendication 9 ou 10, le matériau constituant le renfort fibreux étant à fibres courtes ou longues, de préférence des fibres de verre, du carbone, un polyamide aromatique, du carbure de silicium SiC, des fibres de bambou, du lin, des fibres de coco ou de chanvre.  Electrochemical accumulator according to claim 9 or 10, the material constituting the fiber reinforcement being short or long fibers, preferably glass fibers, carbon, an aromatic polyamide, silicon carbide SiC, bamboo fibers, flax, coconut fiber or hemp.
12. Accumulateur électrochimique selon l'une des revendications précédentes, l'(les) enceinte(s) du (des) caloduc(s) (21) étant de section circulaire ou prismatique.  12. electrochemical accumulator according to one of the preceding claims, the (the) enclosure (s) of (the) pipe (s) (21) being of circular or prismatic section.
13. Accumulateur électrochimique selon l'une des revendications précédentes, la cellule électrochimique C étant sous la forme d'une bobine enroulée autour de l'enceinte (21) du caloduc.  13. Electrochemical accumulator according to one of the preceding claims, the electrochemical cell C being in the form of a coil wound around the enclosure (21) of the heat pipe.
14. Accumulateur électro chimique selon l'une des revendications précédentes, l'enceinte (21) étant agencée en périphérie de la (des) cellules électrochimique(s) C dans un interstice (9) à l'intérieur du premier emballage (3).  Electrochemical accumulator according to one of the preceding claims, the enclosure (21) being arranged on the periphery of the electrochemical cell (s) C in a gap (9) inside the first package (3). .
15. Accumulateur électrochimique selon l'une des revendications précédentes, comportant une pluralité d'un nombre de n premiers emballages (3), dont un nombre égal à n- 1 des premiers emballages (3) loge chacun une cellule électrochimique, les (n-1) premiers emballages étant eux-mêmes logés à l'intérieur de l'autre premier emballage (3).  Electrochemical accumulator according to one of the preceding claims, comprising a plurality of a number of n first packages (3), of which a number equal to n-1 of the first packages (3) each housing an electrochemical cell, the (n -1) first packs being themselves housed inside the other first package (3).
16. Accumulateur électrochimique selon l'une des revendications 1 à 14 comportant au moins un deuxième emballage (3') à base d'alliage métallique, tel qu'un alliage d'aluminium, logeant la(les) cellule(s) électrochimique(s), le deuxième emballage étant lui-même logé de manière étanche dans le premier emballage (3).  16. Electrochemical accumulator according to one of claims 1 to 14 comprising at least a second packaging (3 ') based on a metal alloy, such as an aluminum alloy, housing the electrochemical cell (s) (s) ( s), the second package itself being sealed in the first package (3).
17. Accumulateur électrochimique selon la revendication 16, le premier emballage (3) comportant, sur la couche interne, un revêtement (6) électriquement conducteur.  17. electrochemical accumulator according to claim 16, the first package (3) having, on the inner layer, a coating (6) electrically conductive.
18. Accumulateur électrochimique selon la revendication 17, le revêtement (6) électriquement conducteur étant à base de particules métalliques frittées par frittage photonique ou de graphites conducteurs, de préférence déposé sous forme de peinture ou d'aérosol. Electrochemical accumulator according to Claim 17, the electrically conductive coating (6) being based on sintered metal particles by sintering. photonics or conductive graphites, preferably deposited in the form of paint or aerosol.
19. Accumulateur électrochimique selon l'une des revendications 1 à 15 le premier emballage (3) comportant sur la couche interne un revêtement (6) à fonction de barrière, adapté pour assurer la neutralité chimique de la couche interne (5) vis-à-vis de l'électrolyte de la cellule électrochimique C.  19. electrochemical accumulator according to one of claims 1 to 15 the first package (3) having on the inner layer a coating (6) barrier function, adapted to ensure the chemical neutrality of the inner layer (5) vis-à-vis the electrolyte of the electrochemical cell C.
20. Accumulateur électrochimique selon la revendication 19, le matériau du revêtement (6) barrière étant choisi parmi le polypropylène, le polyéthylène, un polymère de la famille des polyaryléthercétones (PAEK), de préférence le polyétheréthercétone (PEEK™), ou un polymère de la famille des polyimides.  20. Electrochemical accumulator according to claim 19, the material of the coating (6) barrier being selected from polypropylene, polyethylene, a polymer of the family of polyaryletherketones (PAEK), preferably polyetheretherketone (PEEK ™), or a polymer of the family of polyimides.
EP15810636.9A 2014-12-16 2015-12-16 Lithium accumulator with a two-layered thermally insulating package and with a heat pipe for thermal management Withdrawn EP3235022A1 (en)

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FR1462536A FR3030121B1 (en) 2014-12-16 2014-12-16 LITHIUM ACCUMULATOR WITH THERMALLY INSULATED PACKAGING WITH TWO LAYERS AND HEAT TRANSDUCER FOR THERMAL MANAGEMENT
PCT/EP2015/079976 WO2016096974A1 (en) 2014-12-16 2015-12-16 Lithium accumulator with a two-layered thermally insulating package and with a heat pipe for thermal management

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