EP4348757A1 - Use of a cooling composition to protect a battery - Google Patents
Use of a cooling composition to protect a batteryInfo
- Publication number
- EP4348757A1 EP4348757A1 EP22732117.1A EP22732117A EP4348757A1 EP 4348757 A1 EP4348757 A1 EP 4348757A1 EP 22732117 A EP22732117 A EP 22732117A EP 4348757 A1 EP4348757 A1 EP 4348757A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- battery
- cooling
- cooling composition
- composition
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 125
- 238000001816 cooling Methods 0.000 title claims abstract description 111
- 239000012530 fluid Substances 0.000 claims description 35
- 239000002199 base oil Substances 0.000 claims description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 19
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
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- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
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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
- H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
- H01M10/6567—Liquids
- H01M10/6568—Liquids characterised by flow circuits, e.g. loops, located externally to the cells or cell casings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
-
- 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
- H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
- H01M10/625—Vehicles
-
- 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
- H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
- H01M10/6567—Liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the field of compositions for cooling and protecting against the propagation of thermal runaway of a battery and in particular of a lithium-ion battery.
- the battery can be implemented in mobile or stationary applications.
- the invention aims to cool a propulsion system of an electric or hybrid vehicle, and more particularly to cool the battery and possibly the power electronics of an electric or hybrid vehicle. It aims in particular to propose a cooling composition compatible with its implementation at the level of a battery and possibly power electronics.
- a battery is an electrical generating device in which chemical energy is converted into electrical energy.
- the chemical energy consists of electrochemically active compounds deposited on at least one face of electrodes arranged in the electrochemical generator. Electrical energy is produced by electrochemical reactions during a discharge of an electrochemical cell.
- a battery comprises several electrochemical cells.
- a lithium-ion type electrochemical cell is based on the principle of the reversible insertion of lithium into a host structure in an electrochemically active manner.
- the temperature of the cells In the field of electrochemical cells such as lithium-ion cells, the temperature of the cells must be managed in order to maintain the temperature within an adequate range of the cell.
- Lithium-ion batteries are generally implemented at temperatures ranging from -40°C to +70°C. In the event of runaway, some cells can reach temperatures of around 400 to 800°C.
- Stationary applications include storage batteries, for example solar storage batteries.
- mobile applications mention may be made of automotive applications.
- the development of international standards for the reduction of C02 emissions, but also for the reduction of energy consumption, is pushing car manufacturers to offer alternative solutions to combustion engines.
- electric vehicle within the meaning of the present invention, is meant a vehicle comprising an electric motor as sole means of propulsion, whereas a hybrid vehicle comprises a combustion engine and an electric motor as combined means of propulsion.
- propulsion system within the meaning of the present invention, is meant a system comprising the mechanical parts necessary for the propulsion of an electric vehicle.
- the propulsion system thus more specifically includes an electric motor comprising the power electronics rotor-stator assembly (dedicated to speed regulation), a transmission and a battery.
- the battery is itself generally made up of a set of electric accumulators, called cells.
- compositions In general, it is necessary to implement, in electric or hybrid vehicles, compositions to meet the lubrication and/or cooling constraints of the various parts of the propulsion system mentioned above.
- electric propulsion systems generate heat during operation via the electric motor, power electronics and batteries. Since the amount of heat generated is greater than the amount of heat normally dissipated to the environment, it is necessary to ensure cooling of the motor, the power electronics and the batteries. In general, the cooling is carried out on several parts of the propulsion system generating heat and/or the parts of said system sensitive to heat, in order to avoid reaching dangerous temperatures, and in particular the power electronics and batteries.
- application US 2014/0318746 describes the implementation of high thermal conductivity materials in the constituent cells of a battery for electric and/or hybrid vehicles and a low thermal conductivity material for the external casing.
- document US 20120161472 mentions the use of low thermal conductivity materials to form the battery pack and insulate it from the outside.
- This document discloses a fluid based on a water/glycol mixture of very high thermal conductivity.
- the inventors have sought to improve and provide a composition having both improved cooling and thermal runaway protection properties.
- the present invention relates to the use of a cooling composition to protect a battery against thermal runaway, said cooling composition comprising at least one base oil and having a thermal conductivity less than or equal to 125 mW.m fK 1 .
- the battery is a lithium-ion battery.
- the cooling composition implemented according to the invention has a thermal conductivity less than or equal to 120 mW.m fK 1 , preferably less than or equal to 115 mW.ml.K-1.
- the cooling composition implemented according to the invention comprises, relative to the total weight of the cooling composition, at least 70% by weight of base oil(s), preferably from 70 to 99.9% by weight of base oil(s), more preferably from 80 to 99% by weight of base oil(s), more preferably from 85 to 98% by weight of base oil(s) base.
- the cooling composition is implemented in a device for cooling a battery comprising at least one circulation loop in which the cooling composition circulates.
- the cooling composition circulates in at least one element chosen from an oil pump, a fluid exchanger and an air exchanger.
- the cooling device further comprises at least one storage tank for the cooling composition.
- the invention also relates to a device for cooling a battery comprising at least one circulation loop in which the cooling composition according to the invention circulates.
- the cooling composition circulates in at least one element chosen from among an oil pump, a fluid exchanger and an air exchanger.
- the cooling device further comprises at least one storage tank for the cooling composition.
- the battery is a lithium-ion battery.
- the invention also relates to the use of the cooling composition according to the invention, for cooling and for protecting against thermal runaway a battery, preferably a lithium-ion battery.
- the battery is implemented in a propulsion system of an electric or hybrid vehicle, preferably an electric vehicle.
- the cooling composition is implemented in a cooling device as defined in the invention.
- FIG. 1 represents a schematic perspective view of a battery cell as part of the simulation of the experimental part.
- FIG. 2 represents a perspective view of a battery cell and the support (S) within the framework of the simulation of the experimental part.
- FIG. 3 represents a perspective view of a box (B) comprising the cells and the support (S) within the framework of the simulation of the experimental part.
- FIG. 4 represents a top view of a box B within the framework of the simulation of the experimental part.
- FIG. 5 represents a perspective view of a box and the dimensioning (D) for the calculation within the framework of the simulation of the experimental part.
- FIG. 6 represents the evolution of the average temperature of the faulty cell over time, for two fluids and two durations of application of the heat source.
- FIG. 7 represents the evolution of the average temperature of the fluid over time, for two fluids and two durations of application of the heat source.
- FIG. 8 represents the evolution of the average temperature of the neighboring cell over time, for two fluids and two durations of application of the heat source.
- FIG. 9 represents the evolution of the average temperature of the faulty cell over time, for two fluids for a space of 4 mm between two cells.
- FIG. 10 represents the evolution of the average temperature of the fluid over time, for two fluids for a space of 4 mm between two cells.
- FIG. 11 represents the evolution of the mean temperature of the neighboring cell over time, for two fluids for a space of 4 mm between two cells.
- the present invention relates to a composition for cooling and protecting against thermal runaway a propulsion system of an electric or hybrid vehicle, said composition comprising at least one base oil and having a thermal conductivity at 30°C of less than or equal to 125 mW .m fK 1 .
- the cooling composition has a thermal conductivity at 30° C. of less than or equal to 120 mW.m fK 1 , preferably less than or equal to 115 mW.m fK 1 , more preferably less than or equal to 110 mW.m fK 1 .
- the thermal conductivity is measured for example according to the ASTM standard
- the cooling composition implemented according to the invention comprises one or more base oils, preferably in a total content of at least 70% by weight, preferably ranging from 70 to 99% by weight, more preferably 80 to 98% by weight, preferably from 85 to 95% by weight, relative to the total weight of the cooling composition.
- the cooling composition comprises 100% by weight of base oil(s), relative to the total weight of the cooling composition.
- base oils can be chosen from the base oils conventionally used in the field of lubricating oils, such as mineral, synthetic or natural, animal or vegetable oils or mixtures thereof.
- It can be a mixture of several base oils, for example a mixture of two, three, or four base oils.
- the base oils of the cooling compositions considered according to the invention may in particular be oils of mineral or synthetic origin belonging to groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) and presented in Table 1 below or mixtures thereof. [Table 1]
- Mineral base oils include all types of base oils obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, de-alpha removal, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerization and hydrofinishing .
- Blends of synthetic and mineral oils, which may be biosourced, can also be used.
- the base oils of the compositions according to the invention can also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, polyalphaolefins (PAO), and polyalkylene glycol (PAG) obtained by polymerization or copolymerization of alkylene oxides comprising from 2 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.
- synthetic oils such as certain esters of carboxylic acids and alcohols, polyalphaolefins (PAO), and polyalkylene glycol (PAG) obtained by polymerization or copolymerization of alkylene oxides comprising from 2 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.
- the PAOs used as base oils are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene.
- the weight average molecular weight of PAO can vary quite widely. Of preferably, the weight-average molecular mass of the PAO is less than 600 Da.
- the weight-average molecular mass of the PAO can also range from 100 to 600 Da, from 150 to 600 Da, or even from 200 to 600 Da.
- the oil or base oils of the composition according to the invention are chosen from polyalphaolefins (PAO), polyalkylene glycol (PAG) and esters of carboxylic acids and alcohols, silicone , ether.
- PAO polyalphaolefins
- PAG polyalkylene glycol
- esters of carboxylic acids and alcohols silicone , ether.
- Additional additives can be implemented in the cooling composition of the invention.
- these additives mention may be made of antioxidants, anti-corrosion additives, anti-foam additives and pour point depressants.
- the cooling composition implemented according to the invention comprises at least one antioxidant additive.
- the antioxidant additive generally makes it possible to delay the degradation of the composition in service. This degradation can in particular result in the formation of deposits, in the presence of sludge or in an increase in the viscosity of the composition.
- Antioxidant additives act in particular as free radical inhibitors or destroyers of hydroperoxides.
- antioxidant additives commonly employed, mention may be made of antioxidant additives of the phenolic type, antioxidant additives of the amine type, phosphosulfur antioxidant additives. Some of these antioxidant additives, for example phosphosulfur antioxidant additives, can be ash generators.
- the phenolic antioxidant additives may be ash-free or may be in the form of neutral or basic metal salts.
- the antioxidant additives may in particular be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one CI 2 alkyl group, N,N '-dialkyl-aryl-diamines and mixtures thereof.
- the sterically hindered phenols are chosen from compounds comprising a phenol group of which at least one carbon vicinal to the carbon carrying the alcohol function is substituted by at least one Ci-Cio alkyl group, preferably an alkyl group C I -C O , preferably a C4 alkyl group, preferably by the tert-butyl group.
- Amino compounds are another class of antioxidant additives that can be used, possibly in combination with phenolic antioxidant additives.
- amino compounds are aromatic amines, for example aromatic amines of formula NR 4 R 5 R 6 in which R 4 represents an aliphatic group or an optionally substituted aromatic group, R 5 represents an optionally substituted aromatic group, R 6 represents a hydrogen atom, an alkyl group, an aryl group or a group of formula R 7 S(0) z R 8 in which R 7 represents an alkylene group or an alkenylene group, R 8 represents an alkyl group, a alkenyl group or an aryl group and z represents 0, 1 or 2
- Sulfurized alkyl phenols or their alkali and alkaline earth metal salts can also be used as antioxidant additives.
- antioxidant additives are that of copper compounds, for example copper thio- or dithio-phosphates, salts of copper and carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper I and II salts, succinic acid or anhydride salts can also be used.
- copper compounds for example copper thio- or dithio-phosphates, salts of copper and carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates.
- Copper I and II salts, succinic acid or anhydride salts can also be used.
- the cooling composition implemented according to the invention may contain all types of antioxidant additives known to those skilled in the art.
- the cooling composition implemented according to the invention may comprise from 0.1 to 2% by weight of at least one antioxidant additive, relative to the total weight of the composition.
- the cooling composition implemented according to the invention is free of antioxidant additive of aromatic amine type or of sterically hindered phenol type.
- the cooling composition implemented according to the invention may comprise at least one anti-corrosion additive.
- the anti-corrosion additive advantageously makes it possible to delay or prevent the corrosion of the metal parts of the battery.
- a cooling composition implemented according to the invention may comprise from 0.01 to 2% by mass or from 0.01 to 5% by mass, preferably from 0.1 to 1.5% by mass or from 0.1 to 2% by mass of anti-corrosion agent, relative to the total weight of the composition.
- the cooling composition implemented according to the invention may also comprise at least one antifoaming agent.
- the antifoaming agent can be chosen from polyacrylates or even waxes.
- the cooling composition implemented according to the invention may comprise from 0.01 to 2% by weight or from 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight or from 0.1 to 2% mass of antifoaming agent, relative to the total weight of the composition.
- the cooling composition implemented according to the invention may also comprise at least one pour point depressant additive, (also called “PPD” agents for “Pour Point Depressant” in English).
- PPD pour point depressant additive
- pour point depressants By slowing down the formation of paraffin crystals, pour point depressants generally improve the cold behavior of the composition.
- pour point depressant additives mention may be made of polyalkyl methacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, alkylated polystyrenes.
- the cooling composition implemented according to the invention may also further comprise all types of additives suitable for use in a lubricant for a propulsion system of a electric or hybrid vehicle and may be referred to as a lubricating composition.
- Such additives can be chosen from friction modifiers, detergents, anti-wear additives, extreme-pressure additives , dispersants, and mixtures thereof.
- the lubricating composition implemented according to the invention may comprise at least one friction modifier additive.
- the friction modifier additive can be selected from a compound providing metallic elements and a compound free of ash.
- the compounds providing metallic elements mention may be made of complexes of transition metals such as Mo, Sb, Sn, Fe, Cu, Zn, the ligands of which may be hydrocarbon compounds comprising oxygen, nitrogen, sulfur or phosphorus.
- the ash-free friction modifier additives are generally of organic origin and can be chosen from monoesters of fatty acids and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, borate fatty epoxides; fatty amines or fatty acid glycerol esters.
- the fatty compounds comprise at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
- the lubricating composition implemented according to the invention may comprise from 0.01 to 2% by weight or from 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight or from 0.1 to 2% by weight of friction modifier additive, relative to the total weight of the composition.
- the lubricating composition implemented according to the invention may also comprise at least one detergent additive.
- Detergent additives generally reduce the formation of deposits on the surface of metal parts by dissolving secondary products of oxidation and combustion.
- detergent additives that can be used in a lubricating composition used according to the invention are generally known to those skilled in the art.
- Detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head.
- the associated cation can be a metal cation of an alkali or alkaline earth metal.
- the detergent additives are preferably chosen from alkali metal or alkaline-earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, as well as phenate salts.
- the alkali and alkaline-earth metals are preferably calcium, magnesium, sodium or barium.
- These metallic salts generally comprise the metal in a stoichiometric quantity or else in excess, therefore in a quantity greater than the narrow stoichiometric quantity.
- These are then overbased detergent additives; the excess metal bringing the overbased character to the detergent additive is then generally in the form of an oil-insoluble metal salt, for example a carbonate, a hydroxide, an oxalate, an acetate, a glutamate, preferentially a carbonate.
- the lubricating composition implemented according to the invention may for example comprise from 2 to 4% by weight of detergent additive, relative to the total weight of the composition.
- the lubricating composition implemented according to the invention may comprise at least one dispersing agent.
- the dispersing agent can be chosen from Mannich bases, succinimides, for example of the polyisobutylene succinimide type.
- the lubricating composition used according to the invention may, for example, comprise from 0.2 to 10% by weight of dispersing agent(s), relative to the total weight of the composition.
- the lubricating composition used according to the invention may also comprise at least one anti-wear and/or extreme pressure agent.
- the anti-wear additives are chosen from phospho-sulphur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTP.
- phospho-sulphur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTP.
- the preferred compounds are of formula Zn((SP(S)(OR 2 )(OR 3 ))2, in which R 2 and R 3 , which are identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms.
- Amine phosphates are also anti-wear additives which can be used in a composition according to the invention.
- the phosphorus provided by these additives can act as a poison for the catalytic systems of automobiles because these additives generate ash.
- These effects can be minimized by partially replacing the amine phosphates with additives that do not provide phosphorus, such as, for example, polysulphides, in particular sulphur-containing olefins.
- the lubricating composition implemented according to the invention may comprise from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, preferably from 1 to 5% by weight of anti- wear, relative to the total weight of the composition.
- the lubricating composition used according to the invention may also comprise at least one viscosity index improver (VI improver).
- VI improvers include polymethacrylates, polyisobutenes or fatty acid esters. When they are present, these additives can represent from 1 to 25% by weight, of the total weight of the lubricating composition.
- a composition suitable for the invention comprises at least one additional additive chosen from friction modifiers, viscosity index modifiers, detergents, extreme pressure additives, dispersants, antioxidants, anticorrosion additives, pour point depressants, antifoaming agents and mixtures thereof.
- the cooling composition used in the invention comprises less than 0.01% by weight of halocarbon compound(s), preferably the cooling composition used in the invention is free of compound(s) halocarbon(s).
- additives can be introduced separately and/or in the form of a mixture like those already available for sale for the formulations of commercial lubricants for vehicle engines, with a performance level as defined by the ACEA ( Association of European Automobile Manufacturers) and/or the API (American Petroleum Institute), well known to those skilled in the art.
- ACEA Association of European Automobile Manufacturers
- API American Petroleum Institute
- the complementary additive(s) can be added to a base oil or mixture of oils.
- the cooling composition implemented according to the invention has a kinematic viscosity, measured at 40° C. according to the ASTM D445 standard, ranging from 1.5 to 35 mm 2 /s, in particular from 2 to 25 mm 2 /s even from 2.5 to 10 mm 2 /s.
- the cooling composition implemented according to the invention has a kinematic viscosity, measured at 100° C. according to the ASTM D445 standard, ranging from 0.5 to 7 mm 2 /s, in particular from 1 to 4 mm 2 /s or even 1.5 to 2.5 mm 2 /s.
- the cooling composition according to the invention makes it possible to cool the cells of a battery, in particular a lithium-ion battery.
- the battery, in particular lithium-ion can be implemented in a propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
- the cooling composition implemented according to the invention makes it possible to limit or even eliminate the propagation of a thermal runaway when it is implemented in a battery, in particular a lithium-ion battery. More particularly, the battery can be implemented in a propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
- composition according to the invention can be used to cool and/or to protect a battery, in particular a lithium-ion battery, against the propagation of thermal runaway.
- a battery in particular a lithium-ion battery
- the battery can be implemented in a propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
- the cooling composition is implemented at temperatures ranging from -40°C to +70°C, preferably at temperatures ranging from 0 to 30°C.
- composition according to the invention make it possible to define uses according to the invention which are also particular, advantageous or preferred.
- the cooling composition according to the invention can typically circulate in a circulation loop of a cooling device of a propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
- the cooling composition according to the invention will be used to cool and/or to protect against the propagation of a thermal runaway the battery of the propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
- a thermal runaway can be characterized by the damage of a cell (the cell will then be said to be "faulty"), which results in an increase in its internal temperature which will produce exothermic reactions within the electrolyte, which can go as far as an ejection of gas and a discharge of the energy of its chemical reactions in the form of heat.
- This thermal runaway of an isolated cell often results in a propagation of this runaway to the neighboring cell. Indeed, an increase in the temperature of a cell, reaching a temperature of at least 90°C or even at least 100°C or even at least 120°C also causes it to go into thermal runaway.
- a cell will be said to be faulty when its temperature goes above 100°C, or even above 120°C.
- the increase in heat can sometimes be accompanied by an ejection of gas.
- the cooling composition according to the invention can thus be implemented in a circulation loop of a device for cooling a battery.
- the batteries of the invention preferably of the lithium-ion type, can be used at temperatures ranging from -40°C to +70°C, preferably from 0 to 30°C.
- the faulty battery cell can reach temperatures of around 400 to 800°C.
- the present invention also relates to a device for cooling a battery, in particular a lithium-ion battery.
- the battery is implemented in a propulsion system of an electric or hybrid vehicle.
- the cooling device according to the invention comprises at least one circulation loop in which the cooling composition according to the invention circulates.
- the cooling device comprises at least one element selected from an oil pump, a fluid exchanger (heat exchanger between two fluids, also called a “chiller”) and a heat pump.
- the cooling composition according to the invention circulates in at least one chosen element from an oil pump, a chiller and an air exchanger, preferably, in G set of elements chosen from an oil pump, a chiller, and an air exchanger.
- the heat pump can be considered as a heating system or as a refrigeration system.
- the cooling device further comprises a storage tank for the cooling composition.
- the cooling device will preferably be implemented at temperatures ranging from -40°C to +70°C under normal conditions, or even from 0 to +30°C.
- the cooling device according to the invention will make it possible to limit or even avoid thermal runaway in a battery, such as a lithium-ion battery, which can be implemented in a propulsion system of an electric or hybrid vehicle. , preferably an electric vehicle.
- the invention also relates to the use of the cooling composition according to the invention for cooling and/or for protecting against thermal runaway a battery, such as a lithium-ion battery, for example implemented in a propulsion of an electric or hybrid vehicle, preferably an electric vehicle in a cooling device according to the invention.
- a battery such as a lithium-ion battery, for example implemented in a propulsion of an electric or hybrid vehicle, preferably an electric vehicle in a cooling device according to the invention.
- the invention also relates, according to another of its aspects, to a method for cooling a battery, preferably lithium-ion, comprising at least one heat exchange step between the cooling composition according to the invention and at least one piece of said battery.
- the cooling process includes at least one step in which a part of said battery is cooled thanks to the heat exchange step.
- the method is implemented at least in the battery of a propulsion system of an electric or hybrid vehicle, preferably electric.
- the method of cooling a battery does not implement any halocarbon compound(s).
- the process for cooling a battery according to the invention uses a single cooling composition, preferably comprising at least 70% by weight of base oil(s), preferably from 70 to 100% by weight of base oil(s), relative to the total weight of the cooling composition.
- the invention also relates to a method for protecting against thermal backflow of a battery, such as a lithium-ion battery, comprising at least one heat exchange step between the cooling composition according to the invention and at least one piece of said battery.
- the thermal runaway protection method is implemented in the battery of a propulsion system of an electric or hybrid vehicle, preferably an electric vehicle.
- the protection method according to the invention is implemented in a battery comprising several cells and the method comprises at least a step of racing a cell and a step in which the temperature of the neighboring cell does not exceed 120 °C, preferably does not exceed 100°C or even does not exceed 90°C.
- the methods are implemented in the cooling device according to the invention.
- the method of protection against thermal runaway of a battery does not implement halocarbon fluid(s).
- the method for protecting a battery against thermal runaway uses a single cooling composition, preferably comprising at least 70% by weight of base oil(s), preferably 70 to 100% by weight of base oil(s), based on the total weight of the cooling composition.
- a thermal runaway in an electric vehicle battery was simulated using the simulation software: COMSOL MULTIPHYSICS® 5.4, based on the finite element method.
- the modeled battery comprises 5 cells, each identical and of non-deformable rectangular parallelepiped shape with dimensions:
- Fig. 1 represents a view of a cell.
- the properties of the cell support were chosen to represent a copolyester:
- Fig. 2 shows a view of the support (S).
- the box has the following external dimensions:
- Fig. 3 represents a view of the box (B) forming the cells and the support.
- the walls of the box are 2mm thick.
- Fig. 4 shows a top view of a box comprising:
- the geometry of the simulation model has been reduced to the left part of the complete geometry.
- a symmetry condition has been applied at the section plane. This means that the actually simulated geometry differs from the complete geometry. That being said, the heat source being applied in a volumetric manner and the box being closed (no fluid inlet or outlet), this simplification has no qualitative influence on the simulated phenomena and the conclusions drawn from the study.
- the cutting plane is positioned at a distance of 111.375 mm from the left end of the box, positioning it exactly in the middle of the second portion of the support.
- Fig. 5 shows the dimensioning (D) for the calculation.
- the volume of fluid implemented in the domain (D) is 0.936 liters.
- the thermal runaway of the first cell is modeled by the heat source described above.
- the system operates in a closed circuit, the fluid circulates by the sole effect of the modification of the density with the temperature.
- the number of meshes used for the discretization of the model is: 1377265 meshes for the fluid, 2392214 meshes for the cells, 71127 meshes for the box, 1324894 meshes for the support.
- a non-slip condition is applied for the fluid on each surface where it is in contact with a solid (cells or box).
- the box being placed on a support, it is considered that there is no heat exchange between the fluid and the lower part of the box.
- Figs. 6, Figs. 7 and Figs. 8 represents, respectively, the average temperature of the faulty cell (Cl), the average temperature of the fluid, the average temperature of the neighboring cell (C2), for two fluids which are distinguished only by the thermal conductivity, and for two durations different application of the heat source, 10 seconds and 15 seconds.
- the cells are separated by a space of 5 mm.
- Fig. 6 shows that a duration of 15 seconds will cause a greater increase in the temperature of the faulty cell, making it possible to simulate a more severe case of thermal runaway.
- the average temperature of the fluid is lower in the case where the cooling composition according to the invention is implemented.
- the average temperature of the neighboring cell is lower when the cooling composition according to the invention is implemented.
- the cooling composition according to the invention makes it possible, at least to limit, but above all to prevent the propagation of thermal runaway.
- Figs. 10 and Figs. 11 show the effect of the cooling composition according to the invention in cooling and in limiting and preventing the spread of thermal runaway, even under more severe conditions, i.e. 4mm spacing and higher heating of the faulty cell.
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Abstract
The present invention relates to a cooling composition for cooling a battery and protecting it against thermal runaway, the composition having a thermal conductivity lower than or equal to 120 mW.m-1.K-1. The invention also relates to a cooling device and to the use of the cooling composition to cool a battery and/or protect it against thermal runaway, the battery being implemented, for example, in a propulsion system of an electric or hybrid vehicle.
Description
Description Description
Titre : UTILISATION D'UNE COMPOSITION DE REFROIDISSEMENT POUR PROTEGER UNE BATTERIE Domaine technique Title: USE OF A COOLING COMPOSITION TO PROTECT A BATTERY Technical field
La présente invention concerne le domaine des compositions pour refroidir et protéger contre la propagation de remballement thermique d’une batterie et en particulier d’une batterie lithium-ion. La batterie peut être mise en œuvre dans des applications mobiles ou stationnaires. En particulier, l’invention vise à refroidir un système de propulsion d’un véhicule électrique ou hybride, et plus particulièrement à refroidir la batterie et éventuellement l’électronique de puissance d’un véhicule électrique ou hybride. Elle vise en particulier à proposer une composition de refroidissement compatible avec sa mise en œuvre au niveau d’une batterie et éventuellement de l’électronique de puissance. The present invention relates to the field of compositions for cooling and protecting against the propagation of thermal runaway of a battery and in particular of a lithium-ion battery. The battery can be implemented in mobile or stationary applications. In particular, the invention aims to cool a propulsion system of an electric or hybrid vehicle, and more particularly to cool the battery and possibly the power electronics of an electric or hybrid vehicle. It aims in particular to propose a cooling composition compatible with its implementation at the level of a battery and possibly power electronics.
Etat de la technique State of the art
Une batterie est un dispositif de production d’électricité dans lequel de l’énergie chimique est convertie en énergie électrique. L’énergie chimique est constituée par des composés électrochimiquement actifs déposés sur au moins une face d’électrodes disposées dans le générateur électrochimique. L’énergie électrique est produite par des réactions électrochimiques au cours d’une décharge d’une cellule électrochimique. A battery is an electrical generating device in which chemical energy is converted into electrical energy. The chemical energy consists of electrochemically active compounds deposited on at least one face of electrodes arranged in the electrochemical generator. Electrical energy is produced by electrochemical reactions during a discharge of an electrochemical cell.
Une batterie comprend plusieurs cellules électrochimiques. Une cellule électrochimique de type lithium -ion est fondée sur le principe de l’insertion réversible de lithium dans une structure hôte d’une manière électrochimiquement active. A battery comprises several electrochemical cells. A lithium-ion type electrochemical cell is based on the principle of the reversible insertion of lithium into a host structure in an electrochemically active manner.
Dans le domaine des cellules électrochimiques tel que les cellules lithium-ion, la température des cellules doit être gérée afin de maintenir la température à l’intérieur d’une plage adéquate de la cellule. In the field of electrochemical cells such as lithium-ion cells, the temperature of the cells must be managed in order to maintain the temperature within an adequate range of the cell.
Les batteries lithium-ion sont généralement mises en œuvre à des températures allant de -40°C à +70°C. En cas d’emballement, certaines cellules peuvent atteindre des températures de l’ordre de 400 à 800°C. Lithium-ion batteries are generally implemented at temperatures ranging from -40°C to +70°C. In the event of runaway, some cells can reach temperatures of around 400 to 800°C.
Les batteries sont couramment utilisées dans des applications mobiles ou stationnaires. Batteries are commonly used in mobile or stationary applications.
Parmi les applications stationnaires, on peut citer les batteries de stockage, par exemple les batteries de stockage solaire.
Parmi les applications mobiles, on peut citer les applications automobiles. L’évolution des normes internationales pour la réduction des émissions de C02, mais également pour la diminution de la consommation d’énergie, pousse les constructeurs automobiles à proposer des solutions alternatives aux moteurs à combustion. Stationary applications include storage batteries, for example solar storage batteries. Among the mobile applications, mention may be made of automotive applications. The development of international standards for the reduction of C02 emissions, but also for the reduction of energy consumption, is pushing car manufacturers to offer alternative solutions to combustion engines.
L’une des solutions identifiées par les constructeurs automobiles consiste à remplacer les moteurs à combustion par des moteurs électriques. Les recherches pour la réduction des émissions de C02 ont donc mené au développement des véhicules électriques par un certain nombre de compagnies automobiles. One of the solutions identified by car manufacturers is to replace combustion engines with electric motors. Research into reducing C02 emissions has therefore led to the development of electric vehicles by a number of automotive companies.
Par « véhicule électrique » au sens de la présente invention, on entend désigner un véhicule comprenant un moteur électrique comme unique moyen de propulsion alors qu’un véhicule hybride comprend un moteur à combustion et un moteur électrique comme moyens de propulsion combinés. By “electric vehicle” within the meaning of the present invention, is meant a vehicle comprising an electric motor as sole means of propulsion, whereas a hybrid vehicle comprises a combustion engine and an electric motor as combined means of propulsion.
Par « système de propulsion » au sens de la présente invention, on entend désigner un système comprenant les pièces mécaniques nécessaires à la propulsion d’un véhicule électrique. Le système de propulsion englobe ainsi plus particulièrement un moteur électrique comprenant l’ensemble rotor-stator de l’électronique de puissance (dédié à la régulation de la vitesse), une transmission et une batterie. La batterie est elle-même généralement constituée d’un ensemble d’accumulateurs électriques, appelés cellules. By "propulsion system" within the meaning of the present invention, is meant a system comprising the mechanical parts necessary for the propulsion of an electric vehicle. The propulsion system thus more specifically includes an electric motor comprising the power electronics rotor-stator assembly (dedicated to speed regulation), a transmission and a battery. The battery is itself generally made up of a set of electric accumulators, called cells.
D’une manière générale, il est nécessaire de mettre en œuvre, dans les véhicules électriques ou hybrides, des compositions pour répondre aux contraintes de lubrification et/ou de refroidissement des différentes pièces du système de propulsion rappelées ci-dessus. In general, it is necessary to implement, in electric or hybrid vehicles, compositions to meet the lubrication and/or cooling constraints of the various parts of the propulsion system mentioned above.
En particulier, les systèmes de propulsion électriques génèrent de la chaleur pendant leur fonctionnement via le moteur électrique, l’électronique de puissance et les batteries. La quantité de chaleur générée étant supérieure à la quantité de chaleur normalement dissipée à l’environnement, il est nécessaire d’assurer un refroidissement du moteur, de l’électronique de puissance et des batteries. De manière générale, le refroidissement s’effectue sur plusieurs parties du système de propulsion générant de la chaleur et/ou les parties dudit système sensibles à la chaleur, afin d’éviter d’atteindre des températures dangereuses, et notamment l’électronique de puissance et les batteries. In particular, electric propulsion systems generate heat during operation via the electric motor, power electronics and batteries. Since the amount of heat generated is greater than the amount of heat normally dissipated to the environment, it is necessary to ensure cooling of the motor, the power electronics and the batteries. In general, the cooling is carried out on several parts of the propulsion system generating heat and/or the parts of said system sensitive to heat, in order to avoid reaching dangerous temperatures, and in particular the power electronics and batteries.
Traditionnellement, il est connu de refroidir les moteurs électriques par l’air ou par l’eau, éventuellement associée à du glycol. Cependant, avec l’apparition de moteurs de plus en plus petits et dont la puissance est de plus en plus grande, ces méthodes de
refroidissement ne sont plus suffisantes. De plus, la chaleur que peut générer une batterie, notamment lors d’une charge rapide, ne peut être extraite par les méthodes classiquement utilisées sans atteindre des températures endommageant cette dernière (ie > 45°C) et limitant ainsi sa durée de vie. Traditionally, it is known to cool electric motors by air or by water, possibly combined with glycol. However, with the appearance of motors increasingly smaller and whose power is increasingly greater, these methods of cooling are no longer sufficient. In addition, the heat that a battery can generate, in particular during fast charging, cannot be extracted by the methods conventionally used without reaching temperatures that damage the latter (ie > 45° C.) and thus limit its lifetime.
Ainsi, des méthodes alternatives de refroidissement des systèmes de propulsion, en particulier des batteries, ont récemment été proposées. Thus, alternative methods of cooling propulsion systems, in particular batteries, have recently been proposed.
A ce titre, la demande US 2014/0318746 décrit la mise en œuvre de matériaux de haute conductivité thermique au niveau des cellules constitutives d’une batterie pour véhicules électrique et/ou hybride et un matériau de faible conductivité thermique pour le boîtier externe. As such, application US 2014/0318746 describes the implementation of high thermal conductivity materials in the constituent cells of a battery for electric and/or hybrid vehicles and a low thermal conductivity material for the external casing.
Egalement, le document US 20120161472 fait état de la mise en œuvre de matériaux de faible conductivité thermique pour former la pack-batterie et l’isoler de l’extérieur. Ce document divulgue un fluide à base d’un mélange eau/glycol de très haute conductivité thermique. Also, document US 20120161472 mentions the use of low thermal conductivity materials to form the battery pack and insulate it from the outside. This document discloses a fluid based on a water/glycol mixture of very high thermal conductivity.
Alternativement, des sociétés ont travaillé sur le développement de fluides pouvant être utilisés dans des systèmes de propulsion et présentant quant à eux de fortes conductivités thermiques, particulièrement utile pour améliorer le refroidissement au niveau d’une cellule de batterie et donc du système entier. Alternatively, companies have worked on the development of fluids that can be used in propulsion systems and which have high thermal conductivities, particularly useful for improving cooling at the level of a battery cell and therefore of the entire system.
Ainsi, le document WO 2015/034340 décrit des compositions lubrifiantes pour applications automotrices présentant des conductivités thermiques comprises entre 152 et 180 mW.m lK 1. Thus, document WO 2015/034340 describes lubricating compositions for automotive applications having thermal conductivities of between 152 and 180 mW.m lK 1 .
Les inventeurs ont cherché à améliorer et à proposer une composition présentant à la fois des propriétés de refroidissement et de protection contre l’emballement thermique améliorées. The inventors have sought to improve and provide a composition having both improved cooling and thermal runaway protection properties.
Résumé de l’invention Summary of the invention
Plus précisément, la présente invention concerne l’utilisation d’une composition de refroidissement pour protéger une batterie contre l’emballement thermique, ladite composition de refroidissement comprenant au moins une huile de base et présentant une conductivité thermique inférieure ou égale à 125 mW.m fK 1. More specifically, the present invention relates to the use of a cooling composition to protect a battery against thermal runaway, said cooling composition comprising at least one base oil and having a thermal conductivity less than or equal to 125 mW.m fK 1 .
De préférence, la batterie est une batterie lithium-ion.
Selon un mode de réalisation, la composition de refroidissement mise en œuvre selon l’invention présente une conductivité thermique inférieure ou égale à 120 mW.m fK 1, de préférence inférieure ou égale à 115 mW.m-l.K-1. Preferably, the battery is a lithium-ion battery. According to one embodiment, the cooling composition implemented according to the invention has a thermal conductivity less than or equal to 120 mW.m fK 1 , preferably less than or equal to 115 mW.ml.K-1.
Selon un mode de réalisation, la composition de refroidissement mise en œuvre selon l’invention comprend, par rapport au poids total de la composition de refroidissement, au moins 70% en poids d’huile(s) de base, de préférence de 70 à 99,9% en poids d’huile(s) de base, de préférence encore de 80 à 99% en poids d’huile(s) de base, plus préférentiellement de 85 à 98% en poids d’huile(s) de base. According to one embodiment, the cooling composition implemented according to the invention comprises, relative to the total weight of the cooling composition, at least 70% by weight of base oil(s), preferably from 70 to 99.9% by weight of base oil(s), more preferably from 80 to 99% by weight of base oil(s), more preferably from 85 to 98% by weight of base oil(s) base.
De préférence, la composition de refroidissement est mise en œuvre dans un dispositif de refroidissement d’une batterie comprenant au moins une boucle de circulation dans laquelle circule la composition de refroidissement. Preferably, the cooling composition is implemented in a device for cooling a battery comprising at least one circulation loop in which the cooling composition circulates.
De préférence, la composition de refroidissement circule dans au moins un élément choisi parmi une pompe à huile, un échangeur fluide et un échangeur d’air. Preferably, the cooling composition circulates in at least one element chosen from an oil pump, a fluid exchanger and an air exchanger.
De préférence, le dispositif de refroidissement comprend en outre au moins un réservoir de stockage de la composition de refroidissement. Preferably, the cooling device further comprises at least one storage tank for the cooling composition.
L’invention concerne également un dispositif de refroidissement d’une batterie comprenant au moins une boucle de circulation dans laquelle circule la composition de refroidissement selon l’invention. The invention also relates to a device for cooling a battery comprising at least one circulation loop in which the cooling composition according to the invention circulates.
Selon un mode de réalisation du dispositif de refroidissement selon l’invention, la composition de refroidissement circule dans au moins un élément choisi parmi une pompe à huile, un échangeur fluide et un échangeur d’air. According to one embodiment of the cooling device according to the invention, the cooling composition circulates in at least one element chosen from among an oil pump, a fluid exchanger and an air exchanger.
Selon un mode de réalisation, le dispositif de refroidissement comprend en outre au moins un réservoir de stockage de la composition de refroidissement. According to one embodiment, the cooling device further comprises at least one storage tank for the cooling composition.
Selon un mode de réalisation du dispositif de refroidissement selon l’invention, la batterie est une batterie lithium-ion. According to one embodiment of the cooling device according to the invention, the battery is a lithium-ion battery.
L’invention concerne également l’utilisation de la composition de refroidissement selon l’invention, pour refroidir et pour protéger contre l’emballement thermique une batterie, de préférence une batterie lithium-ion. The invention also relates to the use of the cooling composition according to the invention, for cooling and for protecting against thermal runaway a battery, preferably a lithium-ion battery.
Selon un mode de réalisation préféré, la batterie est mise en œuvre dans un système de propulsion d’un véhicule électrique ou hybride, de préférence un véhicule électrique.
Selon un mode de réalisation préféré de G utilisation selon l’invention, la composition de refroidissement est mise en œuvre dans un dispositif de refroidissement telle que défini dans l’invention. According to a preferred embodiment, the battery is implemented in a propulsion system of an electric or hybrid vehicle, preferably an electric vehicle. According to a preferred embodiment of use according to the invention, the cooling composition is implemented in a cooling device as defined in the invention.
Sauf indication contraire, les quantités dans un produit sont exprimées en poids, par rapport au poids total du produit. Unless otherwise indicated, the quantities in a product are expressed by weight, relative to the total weight of the product.
Brève description des dessins Brief description of the drawings
[Fig. 1] représente une vue schématique en perspective d’une cellule de batterie dans le cadre de la simulation de la partie expérimentale. [Fig. 1] represents a schematic perspective view of a battery cell as part of the simulation of the experimental part.
[Fig. 2] représente une vue en perspective d’une cellule de batterie et du support (S) dans le cadre de la simulation de la partie expérimentale. [Fig. 2] represents a perspective view of a battery cell and the support (S) within the framework of the simulation of the experimental part.
[Fig. 3] représente une vue en perspective d’une boite (B) comprenant les cellules et le support (S) dans le cadre de la simulation de la partie expérimentale. [Fig. 3] represents a perspective view of a box (B) comprising the cells and the support (S) within the framework of the simulation of the experimental part.
[Fig. 4] représente une vue du dessus d’une boite B dans le cadre de la simulation de la partie expérimentale. [Fig. 4] represents a top view of a box B within the framework of the simulation of the experimental part.
[Fig. 5] représente une vue en perspective d’une boite et du dimensionnement (D) pour le calcul dans le cadre de la simulation de la partie expérimentale. [Fig. 5] represents a perspective view of a box and the dimensioning (D) for the calculation within the framework of the simulation of the experimental part.
[Fig. 6] représente l’évolution de la température moyenne de la cellule en défaut dans le temps, pour deux fluides et deux durées d’application de la source de chaleur. [Fig. 6] represents the evolution of the average temperature of the faulty cell over time, for two fluids and two durations of application of the heat source.
[Fig. 7] représente l’évolution de la température moyenne du fluide dans le temps, pour deux fluides et deux durées d’application de la source de chaleur. [Fig. 7] represents the evolution of the average temperature of the fluid over time, for two fluids and two durations of application of the heat source.
[Fig. 8] représente l’évolution de la température moyenne de la cellule voisine dans le temps, pour deux fluides et deux durées d’application de la source de chaleur. [Fig. 8] represents the evolution of the average temperature of the neighboring cell over time, for two fluids and two durations of application of the heat source.
[Fig. 9] représente l’évolution de la température moyenne de la cellule en défaut dans le temps, pour deux fluides pour un espace de 4 mm entre deux cellules. [Fig. 9] represents the evolution of the average temperature of the faulty cell over time, for two fluids for a space of 4 mm between two cells.
[Fig. 10] représente l’évolution de la température moyenne du fluide dans le temps, pour deux fluides pour un espace de 4 mm entre deux cellules. [Fig. 10] represents the evolution of the average temperature of the fluid over time, for two fluids for a space of 4 mm between two cells.
[Fig. 11] représente l’évolution de la température moyenne de la cellule voisine dans le temps, pour deux fluides pour un espace de 4 mm entre deux cellules.
Description détaillée [Fig. 11] represents the evolution of the mean temperature of the neighboring cell over time, for two fluids for a space of 4 mm between two cells. detailed description
La présente invention concerne une composition pour refroidir et protéger contre G emballement thermique un système de propulsion d’un véhicule électrique ou hybride, ladite composition comprenant au moins une huile de base et présentant une conductivité thermique à 30°C inférieure ou égale à 125 mW.m fK 1. The present invention relates to a composition for cooling and protecting against thermal runaway a propulsion system of an electric or hybrid vehicle, said composition comprising at least one base oil and having a thermal conductivity at 30°C of less than or equal to 125 mW .m fK 1 .
De préférence, la composition de refroidissement présente une conductivité thermique à 30°C inférieure ou égale à 120 mW.m fK 1, de préférence inférieure ou égale à 115 mW.m fK 1, de préférence encore inférieure ou égale à 110 mW.m fK 1. Preferably, the cooling composition has a thermal conductivity at 30° C. of less than or equal to 120 mW.m fK 1 , preferably less than or equal to 115 mW.m fK 1 , more preferably less than or equal to 110 mW.m fK 1 .
La conductivité thermique est mesurée par exemple selon la norme ASTMThe thermal conductivity is measured for example according to the ASTM standard
D7896. D7896.
Huile (s) de base Base oil(s)
La composition de refroidissement mise en œuvre selon l’invention comprend une ou plusieurs huiles de base, de préférence en une teneur totale d’au moins 70% en poids, de préférence allant de 70 à 99% en poids, de préférence encore de 80 à 98% en poids, préférentiellement de 85 à 95% en poids, par rapport au poids total de la composition de refroidissement. The cooling composition implemented according to the invention comprises one or more base oils, preferably in a total content of at least 70% by weight, preferably ranging from 70 to 99% by weight, more preferably 80 to 98% by weight, preferably from 85 to 95% by weight, relative to the total weight of the cooling composition.
Selon un mode de réalisation, la composition de refroidissement comprend 100% en poids d’huile(s) de base, par rapport au poids total de la composition de refroidissement. According to one embodiment, the cooling composition comprises 100% by weight of base oil(s), relative to the total weight of the cooling composition.
Ces huiles de base peuvent être choisies parmi les huiles de base conventionnellement utilisées dans le domaine des huiles lubrifiantes, telles que les huiles minérales, synthétiques ou naturelles, animales ou végétales ou leurs mélanges. These base oils can be chosen from the base oils conventionally used in the field of lubricating oils, such as mineral, synthetic or natural, animal or vegetable oils or mixtures thereof.
Il peut s’agir d’un mélange de plusieurs huiles de base, par exemple un mélange de deux, trois, ou quatre huiles de base. It can be a mixture of several base oils, for example a mixture of two, three, or four base oils.
Les huiles de base des compositions de refroidissement considérées selon l’invention peuvent être en particulier des huiles d’origines minérales ou synthétiques appartenant aux groupes I à V selon les classes définies dans la classification API (ou leurs équivalents selon la classification ATIEL) et présentées dans le tableau 1 ci-dessous ou leurs mélanges.
[Tableau 1]
The base oils of the cooling compositions considered according to the invention may in particular be oils of mineral or synthetic origin belonging to groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) and presented in Table 1 below or mixtures thereof. [Table 1]
Les huiles de base minérales incluent tous types d’huiles de base obtenues par distillation atmosphérique et sous vide du pétrole brut, suivies d’opérations de raffinage telles qu’ extraction au solvant, désalphatage, déparaffinage au solvant, hydrotraitement, hydrocraquage, hydroisomérisation et hydrofinition. Mineral base oils include all types of base oils obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, de-alpha removal, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerization and hydrofinishing .
Des mélanges d’huiles synthétiques et minérales, pouvant être biosourcées, peuvent également être employés. Blends of synthetic and mineral oils, which may be biosourced, can also be used.
Il n’existe généralement aucune limitation quant à l’emploi d’huiles de base différentes pour réaliser les compositions mises en œuvre selon l’invention, si ce n’est qu’elles doivent avoir des propriétés, notamment en termes de viscosité, d’indice de viscosité, ou de résistance à l’oxydation, adaptées à une utilisation pour des systèmes de propulsion d’un véhicule électrique ou hybride. There is generally no limitation as to the use of different base oils to produce the compositions used according to the invention, except that they must have properties, in particular in terms of viscosity, viscosity index, or resistance to oxidation, suitable for use for propulsion systems of an electric or hybrid vehicle.
Les huiles de bases des compositions selon l’invention peuvent également être choisies parmi les huiles synthétiques, telles certains esters d’acides carboxyliques et d’alcools, les polyalphaoléfines (PAO), et les polyalkylène glycol (PAG) obtenus par polymérisation ou copolymérisation d’oxydes d’alkylène comprenant de 2 à 8 atomes de carbone, en particulier de 2 à 4 atomes de carbone. The base oils of the compositions according to the invention can also be chosen from synthetic oils, such as certain esters of carboxylic acids and alcohols, polyalphaolefins (PAO), and polyalkylene glycol (PAG) obtained by polymerization or copolymerization of alkylene oxides comprising from 2 to 8 carbon atoms, in particular from 2 to 4 carbon atoms.
Les PAO utilisées comme huiles de base sont par exemple obtenues à partir de monomères comprenant de 4 à 32 atomes de carbone, par exemple à partir d’octène ou de décène. La masse moléculaire moyenne en poids de la PAO peut varier assez largement. De
manière préférée, la masse moléculaire moyenne en poids de la PAO est inférieure à 600 Da. La masse moléculaire moyenne en poids de la PAO peut également aller de 100 à 600 Da, de 150 à 600 Da, ou encore de 200 à 600 Da. The PAOs used as base oils are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene. The weight average molecular weight of PAO can vary quite widely. Of preferably, the weight-average molecular mass of the PAO is less than 600 Da. The weight-average molecular mass of the PAO can also range from 100 to 600 Da, from 150 to 600 Da, or even from 200 to 600 Da.
Selon un mode de réalisation préféré, l’huile ou les huiles de base de la composition selon l’invention sont choisies parmi les polyalphaoléfines (PAO), les polyalkylène glycol (PAG) et les esters d’acides carboxyliques et d’alcools, silicone, éther. According to a preferred embodiment, the oil or base oils of the composition according to the invention are chosen from polyalphaolefins (PAO), polyalkylene glycol (PAG) and esters of carboxylic acids and alcohols, silicone , ether.
Additifs complémentaires Complementary additives
Des additifs complémentaires peuvent être mis en œuvre dans la composition de refroidissement de l’invention. Parmi ces additifs, on peut citer les antioxydants, les additifs anti-corrosion, les additifs anti -mousse et les abaisseurs de point d’écoulement. Additional additives can be implemented in the cooling composition of the invention. Among these additives, mention may be made of antioxidants, anti-corrosion additives, anti-foam additives and pour point depressants.
Selon un mode de réalisation particulièrement préféré, la composition de refroidissement mise en œuvre selon l’invention comprend au moins un additif antioxydant. According to a particularly preferred embodiment, the cooling composition implemented according to the invention comprises at least one antioxidant additive.
L’additif antioxydant permet généralement de retarder la dégradation de la composition en service. Cette dégradation peut notamment se traduire par la formation de dépôts, par la présence de boues ou par une augmentation de la viscosité de la composition. The antioxidant additive generally makes it possible to delay the degradation of the composition in service. This degradation can in particular result in the formation of deposits, in the presence of sludge or in an increase in the viscosity of the composition.
Les additifs antioxydants agissent notamment comme inhibiteurs radicalaires ou destructeurs d’hydropéroxydes. Parmi les additifs antioxydants couramment employés, on peut citer les additifs antioxydants de type phénolique, les additifs antioxydants de type aminé, les additifs antioxydants phosphosoufrés. Certains de ces additifs antioxydants, par exemple les additifs antioxydants phosphosoufrés, peuvent être générateurs de cendres. Les additifs antioxydants phénoliques peuvent être exempt de cendres ou bien être sous forme de sels métalliques neutres ou basiques. Les additifs antioxydants peuvent notamment être choisis parmi les phénols stériquement encombrés, les esters de phénol stériquement encombrés et les phénols stériquement encombrés comprenant un pont thioéther, les diphénylamines, les diphénylamines substituées par au moins un groupement alkyle en CI CI 2, les N,N'-dialkyle-aryle-diamines et leurs mélanges. Antioxidant additives act in particular as free radical inhibitors or destroyers of hydroperoxides. Among the antioxidant additives commonly employed, mention may be made of antioxidant additives of the phenolic type, antioxidant additives of the amine type, phosphosulfur antioxidant additives. Some of these antioxidant additives, for example phosphosulfur antioxidant additives, can be ash generators. The phenolic antioxidant additives may be ash-free or may be in the form of neutral or basic metal salts. The antioxidant additives may in particular be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one CI 2 alkyl group, N,N '-dialkyl-aryl-diamines and mixtures thereof.
De préférence selon l’invention, les phénols stériquement encombrés sont choisis parmi les composés comprenant un groupement phénol dont au moins un carbone vicinal du carbone portant la fonction alcool est substitué par au moins un groupement alkyle en Ci- Cio, de préférence un groupement alkyle en CI-CÔ, de préférence un groupement alkyle en C4, de préférence par le groupement tert-butyle.
Les composés aminés sont une autre classe d’additifs antioxydants pouvant être utilisés, éventuellement en combinaison avec les additifs antioxydants phénoliques. Des exemples de composés aminés sont les amines aromatiques, par exemple les amines aromatiques de formule NR4R5R6 dans laquelle R4 représente un groupement aliphatique ou un groupement aromatique, éventuellement substitué, R5 représente un groupement aromatique, éventuellement substitué, R6 représente un atome d’hydrogène, un groupement alkyle, un groupement aryle ou un groupement de formule R7S(0)zR8 dans laquelle R7 représente un groupement alkylène ou un groupement alkenylène, R8 représente un groupement alkyle, un groupement alcényle ou un groupement aryle et z représente 0, 1 ou 2 Preferably according to the invention, the sterically hindered phenols are chosen from compounds comprising a phenol group of which at least one carbon vicinal to the carbon carrying the alcohol function is substituted by at least one Ci-Cio alkyl group, preferably an alkyl group C I -C O , preferably a C4 alkyl group, preferably by the tert-butyl group. Amino compounds are another class of antioxidant additives that can be used, possibly in combination with phenolic antioxidant additives. Examples of amino compounds are aromatic amines, for example aromatic amines of formula NR 4 R 5 R 6 in which R 4 represents an aliphatic group or an optionally substituted aromatic group, R 5 represents an optionally substituted aromatic group, R 6 represents a hydrogen atom, an alkyl group, an aryl group or a group of formula R 7 S(0) z R 8 in which R 7 represents an alkylene group or an alkenylene group, R 8 represents an alkyl group, a alkenyl group or an aryl group and z represents 0, 1 or 2
Des alkyl phénols sulfurisés ou leurs sels de métaux alcalins et alcalino-terreux peuvent également être utilisés comme additifs antioxydants. Sulfurized alkyl phenols or their alkali and alkaline earth metal salts can also be used as antioxidant additives.
Une autre classe d’additifs antioxydants est celle des composés cuivrés, par exemples les thio- ou dithio-phosphates de cuivre, les sels de cuivre et d’acides carboxyliques, les dithiocarbamates, les sulphonates, les phénates, les acétylacétonates de cuivre. Les sels de cuivre I et II, les sels d’acide ou d’anhydride succiniques peuvent également être utilisés. Another class of antioxidant additives is that of copper compounds, for example copper thio- or dithio-phosphates, salts of copper and carboxylic acids, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper I and II salts, succinic acid or anhydride salts can also be used.
La composition de refroidissement mise en œuvre selon l’invention peut contenir tous types d’additifs antioxydants connus de l’homme du métier. The cooling composition implemented according to the invention may contain all types of antioxidant additives known to those skilled in the art.
La composition de refroidissement mise en œuvre selon l’invention peut comprendre de 0,1 à 2 % en poids d’au moins un additif antioxydant, par rapport au poids total de la composition. The cooling composition implemented according to the invention may comprise from 0.1 to 2% by weight of at least one antioxidant additive, relative to the total weight of the composition.
Selon un mode de réalisation particulier, la composition de refroidissement mise en œuvre selon l’invention est exempte d’additif antioxydant de type amine aromatique ou de type phénol stériquement encombré. According to a particular embodiment, the cooling composition implemented according to the invention is free of antioxidant additive of aromatic amine type or of sterically hindered phenol type.
La composition de refroidissement mise en œuvre selon l’invention peut comprendre au moins un additif anticorrosion. The cooling composition implemented according to the invention may comprise at least one anti-corrosion additive.
L’additif anti-corrosion permet avantageusement de retarder ou empêcher la corrosion des pièces métalliques de la batterie. The anti-corrosion additive advantageously makes it possible to delay or prevent the corrosion of the metal parts of the battery.
Une composition de refroidissement mise en œuvre selon l’invention peut comprendre de 0,01 à 2 % massique ou de 0,01 à 5 % massique, préférentiellement de 0,1 à
1,5 % massique ou de 0,1 à 2 % massique d’agent anticorrosion, par rapport au poids total de la composition. A cooling composition implemented according to the invention may comprise from 0.01 to 2% by mass or from 0.01 to 5% by mass, preferably from 0.1 to 1.5% by mass or from 0.1 to 2% by mass of anti-corrosion agent, relative to the total weight of the composition.
La composition de refroidissement mise en œuvre selon l’invention peut comprendre en outre au moins un agent antimousse. The cooling composition implemented according to the invention may also comprise at least one antifoaming agent.
L’agent antimousse peut être choisi parmi les polyacrylates ou encore les cires.The antifoaming agent can be chosen from polyacrylates or even waxes.
La composition de refroidissement mise en œuvre selon l’invention peut comprendre de 0,01 à 2 % massique ou de 0,01 à 5 % massique, préférentiellement de 0,1 à 1,5 % massique ou de 0,1 à 2 % massique d’agent antimousse, par rapport au poids total de la composition. The cooling composition implemented according to the invention may comprise from 0.01 to 2% by weight or from 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight or from 0.1 to 2% mass of antifoaming agent, relative to the total weight of the composition.
La composition de refroidissement mise en œuvre selon l’invention peut également comprendre au moins un additif abaisseur du point d’écoulement, (dits encore agents « PPD » pour « Pour Point Depressant » en langue anglaise). The cooling composition implemented according to the invention may also comprise at least one pour point depressant additive, (also called “PPD” agents for “Pour Point Depressant” in English).
En ralentissant la formation de cristaux de paraffine, les additifs abaisseurs de point d’écoulement améliorent généralement le comportement à froid de la composition. Comme exemple d’additifs abaisseurs de point d’écoulement, on peut citer les polyméthacrylates d’alkyle, les polyacrylates, les polyarylamides, les polyalkylphénols, les polyalkylnaphtalènes, les polystyrènes alkylés. By slowing down the formation of paraffin crystals, pour point depressants generally improve the cold behavior of the composition. As an example of pour point depressant additives, mention may be made of polyalkyl methacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, alkylated polystyrenes.
Lorsque la composition de refroidissement est mise en œuvre dans un système de lubrification, la composition de refroidissement mise en œuvre selon l’invention peut également comprendre en outre tous types d’additifs adaptés à une utilisation dans un lubrifiant pour système de propulsion d’un véhicule électrique ou hybride et pourra être appelée composition lubrifiante. When the cooling composition is implemented in a lubrication system, the cooling composition implemented according to the invention may also further comprise all types of additives suitable for use in a lubricant for a propulsion system of a electric or hybrid vehicle and may be referred to as a lubricating composition.
De tels additifs, connus de l’homme du métier dans le domaine de la lubrification des systèmes de propulsion de véhicules électriques ou hybrides, peuvent être choisis parmi, les modificateurs de frottements, les détergents, les additifs anti usure, les additifs extrême- pression, les dispersants, et leurs mélanges. Such additives, known to those skilled in the art in the field of the lubrication of electric or hybrid vehicle propulsion systems, can be chosen from friction modifiers, detergents, anti-wear additives, extreme-pressure additives , dispersants, and mixtures thereof.
La composition lubrifiante mise en œuvre selon l’invention peut comprendre au moins un additif modificateur de frottement. L’additif modificateur de frottement peut être
choisi parmi un composé apportant des éléments métalliques et un composé exempt de cendres. Parmi les composés apportant des éléments métalliques, on peut citer les complexes de métaux de transition tels que Mo, Sb, Sn, Fe, Cu, Zn dont les ligands peuvent être des composés hydrocarbonés comprenant des atomes d’oxygène, d’azote, de soufre ou de phosphore. Les additifs modificateurs de frottement exempt de cendres sont généralement d’origine organique et peuvent être choisis parmi les monoesters d’acides gras et de polyols, les amines alcoxylées, les amines grasses alcoxylées, les époxydes gras, les époxydes gras de borate ; les amines grasses ou les esters de glycérol d’acide gras. Selon l’invention, les composés gras comprennent au moins un groupement hydrocarboné comprenant de 10 à 24 atomes de carbone. The lubricating composition implemented according to the invention may comprise at least one friction modifier additive. The friction modifier additive can be selected from a compound providing metallic elements and a compound free of ash. Among the compounds providing metallic elements, mention may be made of complexes of transition metals such as Mo, Sb, Sn, Fe, Cu, Zn, the ligands of which may be hydrocarbon compounds comprising oxygen, nitrogen, sulfur or phosphorus. The ash-free friction modifier additives are generally of organic origin and can be chosen from monoesters of fatty acids and polyols, alkoxylated amines, alkoxylated fatty amines, fatty epoxides, borate fatty epoxides; fatty amines or fatty acid glycerol esters. According to the invention, the fatty compounds comprise at least one hydrocarbon group comprising from 10 to 24 carbon atoms.
La composition lubrifiante mise en œuvre selon l’invention peut comprendre de 0,01 à 2 % en poids ou de 0,01 à 5 % en poids, préférentiellement de 0,1 à 1,5 % en poids ou de 0,1 à 2 % en poids d’additif modificateur de frottement, par rapport au poids total de la composition. The lubricating composition implemented according to the invention may comprise from 0.01 to 2% by weight or from 0.01 to 5% by weight, preferably from 0.1 to 1.5% by weight or from 0.1 to 2% by weight of friction modifier additive, relative to the total weight of the composition.
La composition lubrifiante mise en œuvre selon l’invention peut également comprendre au moins un additif détergent. The lubricating composition implemented according to the invention may also comprise at least one detergent additive.
Les additifs détergents permettent généralement de réduire la formation de dépôts à la surface des pièces métalliques par dissolution des produits secondaires d’oxydation et de combustion. Detergent additives generally reduce the formation of deposits on the surface of metal parts by dissolving secondary products of oxidation and combustion.
Les additifs détergents utilisables dans une composition lubrifiante mise en œuvre selon l’invention sont généralement connus de l’homme de métier. Les additifs détergents peuvent être des composés anioniques comprenant une longue chaîne hydrocarbonée lipophile et une tête hydrophile. Le cation associé peut être un cation métallique d’un métal alcalin ou alcalino-terreux. The detergent additives that can be used in a lubricating composition used according to the invention are generally known to those skilled in the art. Detergent additives can be anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation can be a metal cation of an alkali or alkaline earth metal.
Les additifs détergents sont préférentiellement choisis parmi les sels de métaux alcalins ou de métaux alcalino-terreux d’acides carboxyliques, les sulfonates, les salicylates, les naphténates, ainsi que les sels de phénates. Les métaux alcalins et alcalino-terreux sont préférentiellement le calcium, le magnésium, le sodium ou le baryum. The detergent additives are preferably chosen from alkali metal or alkaline-earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, as well as phenate salts. The alkali and alkaline-earth metals are preferably calcium, magnesium, sodium or barium.
Ces sels métalliques comprennent généralement le métal en quantité stœchiométrique ou bien en excès, donc en quantité supérieure à la quantité stœchiom étriqué. Il s’agit alors d’additifs détergents surbasés ; le métal en excès apportant
le caractère surbasé à l’additif détergent est alors généralement sous la forme d’un sel métallique insoluble dans l’huile, par exemple un carbonate, un hydroxyde, un oxalate, un acétate, un glutamate, préférentiellement un carbonate. These metallic salts generally comprise the metal in a stoichiometric quantity or else in excess, therefore in a quantity greater than the narrow stoichiometric quantity. These are then overbased detergent additives; the excess metal bringing the overbased character to the detergent additive is then generally in the form of an oil-insoluble metal salt, for example a carbonate, a hydroxide, an oxalate, an acetate, a glutamate, preferentially a carbonate.
La composition lubrifiante mise en œuvre selon l’invention peut par exemple comprendre de 2 à 4 % en poids d’additif détergent, par rapport au poids total de la composition. The lubricating composition implemented according to the invention may for example comprise from 2 to 4% by weight of detergent additive, relative to the total weight of the composition.
Egalement, la composition lubrifiante mise en œuvre selon l’invention peut comprendre au moins un agent dispersant. Also, the lubricating composition implemented according to the invention may comprise at least one dispersing agent.
L’agent dispersant peut être choisi parmi les bases de Mannich, les succinimides, par exemple de type polyisobutylène succinimide. The dispersing agent can be chosen from Mannich bases, succinimides, for example of the polyisobutylene succinimide type.
La composition lubrifiante mise en œuvre selon l’invention peut par exemple comprendre de 0,2 à 10 % en poids d’agent(s) dispersant(s), par rapport au poids total de la composition. The lubricating composition used according to the invention may, for example, comprise from 0.2 to 10% by weight of dispersing agent(s), relative to the total weight of the composition.
La composition lubrifiante mise en œuvre selon l’invention peut comprendre en outre au moins un agent anti-usure et/ou extrême-pression. The lubricating composition used according to the invention may also comprise at least one anti-wear and/or extreme pressure agent.
Il existe une grande variété d'additifs anti-usure. De manière préférée pour la composition lubrifiante selon l'invention, les additifs anti-usure sont choisis parmi des additifs phospho-soufrés comme les alkylthiophosphates métalliques, en particulier les alkylthiophosphates de zinc, et plus spécifiquement les dialkyldithiophosphates de zinc ou ZnDTP. Les composés préférés sont de formule Zn((SP(S)(OR2)(OR3))2, dans laquelle R2 et R3, identiques ou différents, représentent indépendamment un groupement alkyle, préférentiellement un groupement alkyle comportant de 1 à 18 atomes de carbone. There are a wide variety of anti-wear additives. Preferably, for the lubricating composition according to the invention, the anti-wear additives are chosen from phospho-sulphur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTP. The preferred compounds are of formula Zn((SP(S)(OR 2 )(OR 3 ))2, in which R 2 and R 3 , which are identical or different, independently represent an alkyl group, preferably an alkyl group comprising from 1 to 18 carbon atoms.
Les phosphates d'amines sont également des additifs anti-usure qui peuvent être employés dans une composition selon l'invention. Toutefois, le phosphore apporté par ces additifs peut agir comme poison des systèmes catalytiques des automobiles car ces additifs sont générateurs de cendres. On peut minimiser ces effets en substituant partiellement les phosphates d'amines par des additifs n'apportant pas de phosphore, tels que, par exemple, les polysulfures, notamment les oléfines soufrées.
La composition lubrifiante mise en œuvre selon l’invention peut comprendre de 0,01 à 15% en poids, de préférence de 0,1 à 10% en poids, préférentiellement de 1 à 5% en poids d’agent(s) anti-usure, par rapport au poids total de la composition. Amine phosphates are also anti-wear additives which can be used in a composition according to the invention. However, the phosphorus provided by these additives can act as a poison for the catalytic systems of automobiles because these additives generate ash. These effects can be minimized by partially replacing the amine phosphates with additives that do not provide phosphorus, such as, for example, polysulphides, in particular sulphur-containing olefins. The lubricating composition implemented according to the invention may comprise from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, preferably from 1 to 5% by weight of anti- wear, relative to the total weight of the composition.
La composition lubrifiante mise en œuvre selon l’invention peut également comprendre au moins un additif améliorant l’indice de viscosité (améliorant de VI). Comme exemple d’ améliorant de VI, on peut citer les polyméthacrylates, les polyisobutènes ou les esters d’acide gras. Lorsqu’ils sont présents, ces additifs peuvent représenter de 1 à 25% en poids, du poids total de la composition lubrifiante. The lubricating composition used according to the invention may also comprise at least one viscosity index improver (VI improver). Examples of IV improvers include polymethacrylates, polyisobutenes or fatty acid esters. When they are present, these additives can represent from 1 to 25% by weight, of the total weight of the lubricating composition.
Avantageusement, une composition convenant à l’invention comprend au moins un additif additionnel choisi parmi les modificateurs de frottements, les modificateurs d’indice de viscosité, les détergents, les additifs extrême-pression, les dispersants, les antioxydants, les additifs anticorrosion, les abaisseurs du point d’écoulement, les agents anti mousse et leurs mélanges. Advantageously, a composition suitable for the invention comprises at least one additional additive chosen from friction modifiers, viscosity index modifiers, detergents, extreme pressure additives, dispersants, antioxidants, anticorrosion additives, pour point depressants, antifoaming agents and mixtures thereof.
De préférence, la composition de refroidissement mise en œuvre dans l’invention comprend moins de 0,01% en poids de composé(s) halogénocarbonés, de préférence la omposition de refroidissement mise en œuvre dans l’invention est exempte de composé(s) halogénocarboné(s). Preferably, the cooling composition used in the invention comprises less than 0.01% by weight of halocarbon compound(s), preferably the cooling composition used in the invention is free of compound(s) halocarbon(s).
Ces additifs peuvent être introduits isolément et/ou sous la forme d’un mélange à l’image de ceux déjà disponibles à la vente pour les formulations de lubrifiants commerciaux pour moteurs de véhicules, de niveau de performance tels que définis par l’ ACEA (Association des Constructeurs Européens d’ Automobiles) et/ou l’API (American Petroleum Institute), bien connus de l’homme du métier. These additives can be introduced separately and/or in the form of a mixture like those already available for sale for the formulations of commercial lubricants for vehicle engines, with a performance level as defined by the ACEA ( Association of European Automobile Manufacturers) and/or the API (American Petroleum Institute), well known to those skilled in the art.
En termes de formulation d’une telle composition, le ou les additifs complémentaires peuvent être additionnés à une huile ou mélange d’huiles de base.
Avantageusement, la composition de refroidissement mise en œuvre selon l’invention présente une viscosité cinématique, mesurée à 40°C selon la norme ASTM D445 allant de 1,5 à 35 mm2/s, en particulier de 2 à 25 mm2/s voire de 2,5 à 10 mm2/s. In terms of formulation of such a composition, the complementary additive(s) can be added to a base oil or mixture of oils. Advantageously, the cooling composition implemented according to the invention has a kinematic viscosity, measured at 40° C. according to the ASTM D445 standard, ranging from 1.5 to 35 mm 2 /s, in particular from 2 to 25 mm 2 /s even from 2.5 to 10 mm 2 /s.
Avantageusement, la composition de refroidissement mise en œuvre selon l’invention présente une viscosité cinématique, mesurée à 100°C selon la norme ASTM D445 allant de 0,5 à 7 mm2/s, en particulier de 1 à 4 mm2/s voire de 1,5 à 2,5 mm2/s. Advantageously, the cooling composition implemented according to the invention has a kinematic viscosity, measured at 100° C. according to the ASTM D445 standard, ranging from 0.5 to 7 mm 2 /s, in particular from 1 to 4 mm 2 /s or even 1.5 to 2.5 mm 2 /s.
La composition de refroidissement selon l’invention permet de refroidir les cellules d’une batterie, en particulier une batterie lithium-ion. La batterie, en particulier lithium-ion peut être mise en œuvre dans un système de propulsion d’un véhicule électrique ou hybride, en particulier d’un véhicule électrique. The cooling composition according to the invention makes it possible to cool the cells of a battery, in particular a lithium-ion battery. The battery, in particular lithium-ion, can be implemented in a propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
La composition de refroidissement mise en œuvre selon l’invention permet de limiter voire de supprimer la propagation d’un emballement thermique lorsqu’elle est mise en œuvre dans une batterie, en particulier une batterie lithium-ion. Plus particulièrement, la batterie peut être mise en œuvre dans un système de propulsion d’un véhicule électrique ou hybride, en particulier d’un véhicule électrique. The cooling composition implemented according to the invention makes it possible to limit or even eliminate the propagation of a thermal runaway when it is implemented in a battery, in particular a lithium-ion battery. More particularly, the battery can be implemented in a propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
Ainsi, la composition selon l’invention peut être utilisée pour refroidir et/ou pour protéger contre la propagation d’un emballement thermique une batterie, en particulier une batterie lithium-ion. Plus particulièrement, la batterie peut être mise en œuvre dans un système de propulsion d’un véhicule électrique ou hybride, en particulier d’un véhicule électrique. Thus, the composition according to the invention can be used to cool and/or to protect a battery, in particular a lithium-ion battery, against the propagation of thermal runaway. More particularly, the battery can be implemented in a propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
Typiquement, la composition de refroidissement est mise en œuvre à des températures allant de -40°C à +70°C, de préférence à des températures allant de 0 à 30°C. Typically, the cooling composition is implemented at temperatures ranging from -40°C to +70°C, preferably at temperatures ranging from 0 to 30°C.
Selon l'invention, les caractéristiques particulières, avantageuses ou préférées de la composition selon l'invention, permettent de définir des utilisations selon l'invention qui sont également particulières, avantageuses ou préférées. According to the invention, the particular, advantageous or preferred characteristics of the composition according to the invention make it possible to define uses according to the invention which are also particular, advantageous or preferred.
La composition de refroidissement selon l’invention pourra typiquement circuler dans une boucle de circulation d’un dispositif de refroidissement d’un système de propulsion d’un véhicule électrique ou hybride, en particulier d’un véhicule électrique. The cooling composition according to the invention can typically circulate in a circulation loop of a cooling device of a propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
Selon un mode de réalisation préférée, la composition de refroidissement selon l’invention sera utilisée pour refroidir et/ou pour protéger contre la propagation d’un
emballement thermique la batterie du système de propulsion d’un véhicule électrique ou hybride, en particulier d’un véhicule électrique. According to a preferred embodiment, the cooling composition according to the invention will be used to cool and/or to protect against the propagation of a thermal runaway the battery of the propulsion system of an electric or hybrid vehicle, in particular of an electric vehicle.
Généralement, dans le cas d’une batterie comportant plusieurs cellules, un emballement thermique peut se caractériser par l’endommagement d’une cellule (la cellule sera alors dite « en défaut ») ce qui a pour conséquence une augmentation de sa température interne qui va produire des réactions exothermiques au sein de l’électrolyte, pouvant aller jusqu’à une éjection de gaz et une décharge de l’énergie de ses réactions chimiques sous forme de chaleur. Generally, in the case of a battery comprising several cells, a thermal runaway can be characterized by the damage of a cell (the cell will then be said to be "faulty"), which results in an increase in its internal temperature which will produce exothermic reactions within the electrolyte, which can go as far as an ejection of gas and a discharge of the energy of its chemical reactions in the form of heat.
Cet emballement thermique d’une cellule isolée a souvent comme conséquence une propagation de cet emballement à la cellule voisine. En effet, une augmentation de la température d’une cellule, en atteignant une température d’au moins 90°C voire d’au moins 100°C voire d’au moins 120°C la fait partir également en emballement thermiqueThis thermal runaway of an isolated cell often results in a propagation of this runaway to the neighboring cell. Indeed, an increase in the temperature of a cell, reaching a temperature of at least 90°C or even at least 100°C or even at least 120°C also causes it to go into thermal runaway.
Typiquement, une cellule sera dite en défaut lorsque sa température va au-delà de 100°C, voire au-delà de 120°C. L’augmentation de chaleur peut parfois s’accompagner d’une éjection de gaz. Typically, a cell will be said to be faulty when its temperature goes above 100°C, or even above 120°C. The increase in heat can sometimes be accompanied by an ejection of gas.
La composition de refroidissement selon l’invention peut ainsi être mise en œuvre dans une boucle de circulation d’un dispositif de refroidissement d’une batterie. The cooling composition according to the invention can thus be implemented in a circulation loop of a device for cooling a battery.
Les batteries de l’invention, de préférence de type lithium-ion, peuvent mises en œuvre à des températures allant de -40°C à +70°C, de préférence de 0 à 30°C. The batteries of the invention, preferably of the lithium-ion type, can be used at temperatures ranging from -40°C to +70°C, preferably from 0 to 30°C.
En cas d’emballement, la cellule en défaut de la batterie peut atteindre des températures de l’ordre de 400 à 800°C. In the event of runaway, the faulty battery cell can reach temperatures of around 400 to 800°C.
La présente invention concerne également un dispositif de refroidissement d’une batterie, en particulier une batterie lithium-ion. Selon un mode de réalisation préférence, la batterie est mise en œuvre dans un système de propulsion d’un véhicule électrique ou hybride. The present invention also relates to a device for cooling a battery, in particular a lithium-ion battery. According to a preferred embodiment, the battery is implemented in a propulsion system of an electric or hybrid vehicle.
Le dispositif de refroidissement selon l’invention comprend au moins une boucle de circulation dans laquelle circule la composition de refroidissement selon l’invention. The cooling device according to the invention comprises at least one circulation loop in which the cooling composition according to the invention circulates.
Typiquement, le dispositif de refroidissement comprend au moins un élément choisi parmi une pompe à huile, un échangeur fluide (échangeur de chaleur entre deux fluides, aussi appelé « chiller ») et une pompe à chaleur. Ainsi, selon un mode de réalisation, la composition de refroidissement selon l’invention circule dans au moins un élément choisi
parmi une pompe à huile, un chiller et un échangeur à air, de préférence, dans G ensemble des éléments choisis parmi une pompe à huile, un chiller, et un échangeur à air. Typically, the cooling device comprises at least one element selected from an oil pump, a fluid exchanger (heat exchanger between two fluids, also called a “chiller”) and a heat pump. Thus, according to one embodiment, the cooling composition according to the invention circulates in at least one chosen element from an oil pump, a chiller and an air exchanger, preferably, in G set of elements chosen from an oil pump, a chiller, and an air exchanger.
Au sens de la présente invention, la pompe à chaleur peut être considérée comme un système de chauffage ou comme un système de réfrigération. Within the meaning of the present invention, the heat pump can be considered as a heating system or as a refrigeration system.
Généralement, le dispositif de refroidissement comprend en outre un réservoir de stockage de la composition de refroidissement. Generally, the cooling device further comprises a storage tank for the cooling composition.
Le dispositif de refroidissement sera de préférence mis en œuvre à des température allant de -40°C à +70°C dans des conditions normales, voire de 0 à +30°C. The cooling device will preferably be implemented at temperatures ranging from -40°C to +70°C under normal conditions, or even from 0 to +30°C.
Le dispositif de refroidissement selon l’invention permettra de limiter voire d’éviter l’emballement thermique dans une batterie, telle qu’une batterie lithium -ion, qui pourra être mise en œuvre dans un système de propulsion d’un véhicule électrique ou hybride, de préférence d’un véhicule électrique. The cooling device according to the invention will make it possible to limit or even avoid thermal runaway in a battery, such as a lithium-ion battery, which can be implemented in a propulsion system of an electric or hybrid vehicle. , preferably an electric vehicle.
L’invention concerne également l’utilisation de la composition de refroidissement selon l’invention pour refroidir et/ou pour protéger contre l’emballement thermique une batterie, telle qu’une batterie lithium-ion, par exemple mise en œuvre dans un système de propulsion d’un véhicule électrique ou hybride, de préférence un véhicule électrique dans un dispositif de refroidissement selon l’invention. The invention also relates to the use of the cooling composition according to the invention for cooling and/or for protecting against thermal runaway a battery, such as a lithium-ion battery, for example implemented in a propulsion of an electric or hybrid vehicle, preferably an electric vehicle in a cooling device according to the invention.
L’invention concerne encore, selon un autre de ses aspects, un procédé de refroidissement d’une batterie, de préférence lithium-ion, comprenant au moins une étape d’échange thermique entre la composition de refroidissement selon l’invention et au moins une pièce de ladite batterie. Typiquement, le procédé de refroidissement comprend au moins une étape dans laquelle une pièce de ladite batterie est refroidie grâce à l’étape d’échange thermique. De préférence, le procédé est mis en œuvre au moins dans la batterie d’un système de propulsion d’un véhicule électrique ou hybride, de préférence électrique. The invention also relates, according to another of its aspects, to a method for cooling a battery, preferably lithium-ion, comprising at least one heat exchange step between the cooling composition according to the invention and at least one piece of said battery. Typically, the cooling process includes at least one step in which a part of said battery is cooled thanks to the heat exchange step. Preferably, the method is implemented at least in the battery of a propulsion system of an electric or hybrid vehicle, preferably electric.
Ainsi, selon un mode de réalisation préféré, le procédé de refroidissement d’une batterie, de préférence lithium-ion, ne met pas en œuvre de compos(é) halogénocarboné(s). Thus, according to a preferred embodiment, the method of cooling a battery, preferably lithium-ion, does not implement any halocarbon compound(s).
Plus spécifiquement, le procédé de refroidissement d’une batterie selon l’invention met en œuvre une unique composition de refroidissement, comprenant de préférence au moins 70% en poids d’huile(s) de base, de préférence de 70 à 100% en poids d’huile(s) de base, par rapport au poids total de la composition de refroidissement.
L’invention concerne également un procédé de protection contre remballement thermique d’une batterie, telle qu’une batterie lithium-ion, comprenant au moins une étape d’échange thermique entre la composition de refroidissement selon l’invention et au moins une pièce de ladite batterie. De préférence, le procédé de protection contre l’emballement thermique est mis en œuvre dans la batterie d’un système de propulsion d’un véhicule électrique ou hybride, de préférence un véhicule électrique. Typiquement, le procédé de protection selon l’invention est mis en œuvre dans une batterie comportant plusieurs cellules et le procédé comprend au moins une étape d’emballement d’une cellule et une étape dans laquelle la température de la cellule voisine ne dépasse pas 120°C, de préférence ne dépasse pas 100°C voire ne dépasse pas 90°C. More specifically, the process for cooling a battery according to the invention uses a single cooling composition, preferably comprising at least 70% by weight of base oil(s), preferably from 70 to 100% by weight of base oil(s), relative to the total weight of the cooling composition. The invention also relates to a method for protecting against thermal backflow of a battery, such as a lithium-ion battery, comprising at least one heat exchange step between the cooling composition according to the invention and at least one piece of said battery. Preferably, the thermal runaway protection method is implemented in the battery of a propulsion system of an electric or hybrid vehicle, preferably an electric vehicle. Typically, the protection method according to the invention is implemented in a battery comprising several cells and the method comprises at least a step of racing a cell and a step in which the temperature of the neighboring cell does not exceed 120 °C, preferably does not exceed 100°C or even does not exceed 90°C.
De préférence, les procédés sont mis en œuvre dans le dispositif de refroidissement selon l’invention. Preferably, the methods are implemented in the cooling device according to the invention.
Ainsi, selon un mode de réalisation préféré, le procédé de protection contre l’emballement thermique d’une batterie, de préférence lithium-ion, ne met pas en œuvre de fluide(s) halogénocarboné(s). Thus, according to a preferred embodiment, the method of protection against thermal runaway of a battery, preferably lithium-ion, does not implement halocarbon fluid(s).
Plus spécifiquement, le procédé de protection contre l’emballement thermique d’une batterie selon l’invention met en œuvre une unique composition de refroidissement, comprenant de préférence au moins 70% en poids d’huile(s) de base, de préférence de 70 à 100% en poids d’huile(s) de base, par rapport au poids total de la composition de refroidissement. More specifically, the method for protecting a battery against thermal runaway according to the invention uses a single cooling composition, preferably comprising at least 70% by weight of base oil(s), preferably 70 to 100% by weight of base oil(s), based on the total weight of the cooling composition.
L’ensemble des caractéristiques et préférences décrites pour la composition de refroidissement selon l’invention ainsi que pour ses utilisations s’applique également à ce procédé. All of the characteristics and preferences described for the cooling composition according to the invention as well as for its uses also apply to this process.
L’invention va maintenant être décrite au moyen des exemples suivants, donnés bien entendu à titre illustratif et non limitatif de l’invention. The invention will now be described by means of the following examples, given of course by way of non-limiting illustration of the invention.
Exemples Examples
Un emballement thermique dans une batterie de véhicule électrique a été simulée à l’aide du logiciel de simulation : COMSOL MULTIPHYSICS® 5.4, basé sur la méthode des éléments finis.
La batterie modélisée comprend 5 cellules, chacune identique et de forme parallélépipède rectangle non déformable de dimension : A thermal runaway in an electric vehicle battery was simulated using the simulation software: COMSOL MULTIPHYSICS® 5.4, based on the finite element method. The modeled battery comprises 5 cells, each identical and of non-deformable rectangular parallelepiped shape with dimensions:
- Longueur L (dimension x) = 250mm, - Length L (dimension x) = 250mm,
- largeur 1 (dimension z) = 198mm et - width 1 (dimension z) = 198mm and
- épaisseur e (dimension y) = 5mm. - thickness e (dimension y) = 5mm.
La Fig. 1 représente une vue d’une cellule. Fig. 1 represents a view of a cell.
Les propriétés de ces cellules sont les suivantes : The properties of these cells are as follows:
- Masse volumique (densité): rho = 2700 kg/m3 - Density (density): rho = 2700 kg/m 3
- Capacité calorifique massique: Cp = 900 J/(kg.K); - Mass heat capacity: Cp = 900 J/(kg.K);
- Conductivité thermique anisotrope: kxx = kzz = 35 W/(m.K), kyy = 0.8 W/(m.K). - Anisotropic thermal conductivity: kxx = kzz = 35 W/(m.K), kyy = 0.8 W/(m.K).
Une source de chaleur volumique est appliquée à la première cellule (celle subissant un emballement thermique). Cette source a été calculée pour faire monter la température de la cellule en défaut à environ 800°C (en partant d’une température de 30°C) en l’espace de 10s. Le calcul utilisé est le suivant : Q = rho*Cp*différence de température/durée de l’emballement. Cela donne une valeur de source de chaleur constante de 1,871 le8 W/m3. Cette valeur a été conservée dans le cas où l’emballement dure 15s, la cellule en défaut recevant donc dans ce cas plus d’énergie que dans le cas où l’emballement dure 10s (facteur 1,5). A source of bulk heat is applied to the first cell (the one undergoing thermal runaway). This source has been calculated to raise the temperature of the faulty cell to about 800°C (starting from a temperature of 30°C) in the space of 10s. The calculation used is as follows: Q = rho*Cp*difference in temperature/runaway duration. This gives a constant heat source value of 1.871 le8 W/m 3 . This value was kept in the case where the runaway lasts 15s, the faulty cell therefore receiving in this case more energy than in the case where the runaway lasts 10s (factor 1.5).
Dans ces essais, l’effet de la conductivité thermique a été évalué. Ainsi, seul ce paramètre a été modifié d’un fluide (composition de refroidissement) à l’autre, en utilisant la loi de comportement : In these tests, the effect of thermal conductivity was evaluated. Thus, only this parameter has been modified from one fluid (cooling composition) to another, using the constitutive law:
- Pour le fluide ayant une conductivité thermique de 110 W/(m.K), on utilise: k = -0,21*T + 116,35 - For the fluid having a thermal conductivity of 110 W/(m.K), we use: k = -0.21*T + 116.35
- Pour le fluide ayant une conductivité thermique de 140 W/(m.K), on utilise: k = -0,21*T + 146,35 - For the fluid having a thermal conductivity of 140 W/(m.K), we use: k = -0.21*T + 146.35
Les propriétés du support des cellules ont été choisies pour représenter un copolyester :The properties of the cell support were chosen to represent a copolyester:
- Masse volumique : rho = 1130 kg/m3 - Density: rho = 1130 kg/m 3
- Capacité calorifique massique : Cp = 1600 J/(kg.K); - Mass heat capacity: Cp = 1600 J/(kg.K);
- Conductivité thermique isotrope : k = 0.19 W/(m.K).
La Fig. 2 représente une vue du support (S). - Isotropic thermal conductivity: k = 0.19 W/(mK). Fig. 2 shows a view of the support (S).
La boite a les dimensions extérieures suivantes : The box has the following external dimensions:
- L = 274 mm; - L = 274mm;
- 1 = 231 mm - 1 = 231mm
- e = 64 mm. - e = 64 mm.
La Fig. 3 représente une vue de la boite (B) renformant les cellules et le support. Fig. 3 represents a view of the box (B) forming the cells and the support.
Les parois de la boîte ont une épaisseur de 2mm. The walls of the box are 2mm thick.
Ses propriétés correspondent à de l’acier et sont les suivantes : Its properties correspond to steel and are as follows:
- Masse volumique : rho = 7850 kg/m3 - Density: rho = 7850 kg/m 3
- Capacité calorifique massique : Cp = 475 J/(kg.K); - Mass heat capacity: Cp = 475 J/(kg.K);
- Conductivité thermique isotrope : k = 44.5 W/(m.K). - Isotropic thermal conductivity: k = 44.5 W/(m.K).
La Fig. 4 représente une vue du dessus d’une boite comprenant : Fig. 4 shows a top view of a box comprising:
- 5 cellules : Cl, C2, C3, C4 et C5 - 5 cells: Cl, C2, C3, C4 and C5
- 4 espacements remplis d’un fluide : Fl, F2, F3, F4, entre chaque cellule. - 4 spaces filled with a fluid: Fl, F2, F3, F4, between each cell.
Pour les essais de simulation, c’est la cellule Cl qui a été mise en défaut (par application de la source de chaleur). For the simulation tests, cell C1 was faulty (by application of the heat source).
Afin de limiter la taille du problème à résoudre, la géométrie du modèle de simulation a été réduite à la partie gauche de la géométrie complète. Une condition de symétrie a été appliquée au niveau du plan de coupe. Cela signifie que la géométrie réellement simulée diffère de la géométrie complète. Ceci étant, la source de chaleur étant appliquée de manière volumique et la boite étant fermée (pas d’entrée ou de sortie de fluide), cette simplification n’a aucune influence qualitative sur les phénomènes simulés et les conclusions tirées de l’étude. Le plan de coupe est positionné à une distance de 111,375 mm de l’extrémité gauche de la boite le positionnant exactement au milieu de la seconde portion du support. In order to limit the size of the problem to be solved, the geometry of the simulation model has been reduced to the left part of the complete geometry. A symmetry condition has been applied at the section plane. This means that the actually simulated geometry differs from the complete geometry. That being said, the heat source being applied in a volumetric manner and the box being closed (no fluid inlet or outlet), this simplification has no qualitative influence on the simulated phenomena and the conclusions drawn from the study. The cutting plane is positioned at a distance of 111.375 mm from the left end of the box, positioning it exactly in the middle of the second portion of the support.
La Fig. 5 montre le dimensionnement (D) pour le calcul. Le volume de fluide mis en œuvre dans le domaine (D) est de 0,936 litres. Fig. 5 shows the dimensioning (D) for the calculation. The volume of fluid implemented in the domain (D) is 0.936 liters.
La modélisation physique se caractérise par les éléments suivants : The physical modeling is characterized by the following elements:
- Le couplage fort (i.e. l’écoulement influence les transferts thermiques via le terme
d’advection et la thermique influence l’écoulement par la dépendance des propriétés de fluide à la température) entre les équations de Navier-Stokes décrivant l’écoulement et de l’équation de la chaleur représentant les transferts thermiques dans le fluide. - The strong coupling (ie the flow influences the thermal transfers via the term advection and thermal influences the flow by the dependence of fluid properties on temperature) between the Navier-Stokes equations describing the flow and the heat equation representing the heat transfers in the fluid.
- L’équation de la chaleur dans l’ensemble des solides pour représenter les transferts thermiques dans les solides. - The equation of heat in all solids to represent heat transfer in solids.
- Le fluide est considéré comme incompressible (seule l’influence de la thermique sur la masse volumique est prise en compte, il s’agit de l’approximation de Boussinesq). - The fluid is considered as incompressible (only the influence of thermics on the density is taken into account, this is the Boussinesq approximation).
- L’emballement thermique de la première cellule est modélisé par la source de chaleur décrite précédemment. - The thermal runaway of the first cell is modeled by the heat source described above.
- le système fonctionne en circuit fermé, le fluide circule par l’unique effet de la modification de la masse volumique avec la température. - the system operates in a closed circuit, the fluid circulates by the sole effect of the modification of the density with the temperature.
- le nombre de mailles utilisées pour la discrétisation du modèle est : 1377265 mailles pour le fluide, 2392214 mailles pour les cellules, 71127 mailles pour la boite, 1324894 mailles pour le support. - the number of meshes used for the discretization of the model is: 1377265 meshes for the fluid, 2392214 meshes for the cells, 71127 meshes for the box, 1324894 meshes for the support.
Dans le cadre de ces essais, une condition de non-glissement est appliquée pour le fluide sur chaque surface où celui-ci est en contact avec un solide (cellules ou boîte). La surface supérieure du domaine fluide est par contre une surface libre sur laquelle des vitesses tangentielles sont autorisées. D’un point de vue thermique, la surface libre du fluide ainsi que l’ensemble des surfaces extérieures de la boite (sauf la surface inférieure) échange de la chaleur avec l’air extérieur (qui est à 30°C) avec un coefficient d’échange h = 10 W/(m2.K). La boite étant posée sur un support, on considère qu’il n’y a pas d’échange de chaleur entre le fluide et la partie basse de la boite. As part of these tests, a non-slip condition is applied for the fluid on each surface where it is in contact with a solid (cells or box). The upper surface of the fluid domain is on the other hand a free surface on which tangential velocities are authorized. From a thermal point of view, the free surface of the fluid as well as all the external surfaces of the box (except the lower surface) exchange heat with the external air (which is at 30°C) with a coefficient of exchange h = 10 W/(m 2 .K). The box being placed on a support, it is considered that there is no heat exchange between the fluid and the lower part of the box.
Les Fig. 6, Fig. 7 et Fig. 8 représente, respectivement, la température moyenne de la cellule en défaut (Cl), la température moyenne du fluide, la température moyenne de la cellule voisine (C2), pour deux fluides qui se distinguent uniquement par la conductivité thermique, et pour deux durées différentes d’application de la source de chaleur, 10 secondes et 15 secondes. Pour les résultats illustrés sur ces 3 figures, les cellules sont séparées par un espace de 5 mm.
La Fig. 6 montre qu’une durée de 15 secondes provoquera une augmentation plus importante de la température de la cellule en défaut, permettant de simuler un cas plus sévère d’emballement thermique. Comme le montrent les résultats de la Fig. 7, la température moyenne du fluide est plus faible dans le cas où la composition de refroidissement selon l’invention est mise en œuvre. Comme le montrent les résultats de la Fig. 8, la température moyenne de la cellule voisine est plus faible lorsque la composition de refroidissement selon l’invention est mise en œuvre. Ainsi, la composition de refroidissement selon l’invention permet, a minima de limiter, mais surtout d’empêcher la propagation de l’emballement thermique. Figs. 6, Figs. 7 and Figs. 8 represents, respectively, the average temperature of the faulty cell (Cl), the average temperature of the fluid, the average temperature of the neighboring cell (C2), for two fluids which are distinguished only by the thermal conductivity, and for two durations different application of the heat source, 10 seconds and 15 seconds. For the results illustrated in these 3 figures, the cells are separated by a space of 5 mm. Fig. 6 shows that a duration of 15 seconds will cause a greater increase in the temperature of the faulty cell, making it possible to simulate a more severe case of thermal runaway. As shown by the results in Fig. 7, the average temperature of the fluid is lower in the case where the cooling composition according to the invention is implemented. As shown by the results in Fig. 8, the average temperature of the neighboring cell is lower when the cooling composition according to the invention is implemented. Thus, the cooling composition according to the invention makes it possible, at least to limit, but above all to prevent the propagation of thermal runaway.
D’autres essais ont été mis en œuvre mais cette fois-ci avec un espace de 4 mm entre deux cellules et une durée de 15s. Un espacement plus faible entre deux cellules est plus propice à la propagation de l’emballement thermique. Les résultats sont illustrés sur les Fig. 9 (température moyenne de la cellule en défaut), Fig. 10 (température moyenne du fluide) et Fig. 11 (température moyenne de la cellule voisine). Other tests were implemented but this time with a space of 4 mm between two cells and a duration of 15s. A smaller spacing between two cells is more conducive to the propagation of thermal runaway. The results are illustrated in Figs. 9 (average temperature of the faulty cell), FIG. 10 (mean fluid temperature) and Fig. 11 (average temperature of the neighboring cell).
Les résultats des Fig. 10 et Fig. 11 montrent l’effet de la composition de refroidissement selon l’invention pour refroidir et pour limiter et pour empêcher la propagation de l’emballement thermique, même dans des conditions plus sévères, à savoir 4mm d’espacement et un chauffage plus élevé de la cellule en défaut.
The results of Figs. 10 and Figs. 11 show the effect of the cooling composition according to the invention in cooling and in limiting and preventing the spread of thermal runaway, even under more severe conditions, i.e. 4mm spacing and higher heating of the faulty cell.
Claims
1. Utilisation d’une composition de refroidissement pour protéger une batterie contre remballement thermique, ladite composition de refroidissement comprenant au moins une huile de base et présentant une conductivité thermique inférieure ou égale à 125 mW.m lK 1. 1. Use of a cooling composition to protect a battery against thermal backflow, said cooling composition comprising at least one base oil and having a thermal conductivity less than or equal to 125 mW.m lK 1 .
2. Utilisation selon la revendication 1, dans laquelle la composition de refroidissement présente une conductivité thermique inférieure ou égale à 120 mW.m lK 1, de préférence inférieure ou égale à 115 mW.m fK 1. 2. Use according to claim 1, in which the cooling composition has a thermal conductivity of less than or equal to 120 mW.m fK 1 , preferably less than or equal to 115 mW.m fK 1 .
3. Utilisation selon la revendication 1 ou 2, dans laquelle la composition de refroidissement comprend, par rapport au poids total de la composition de refroidissement, au moins 70% en poids d’huile(s) de base, de préférence de 70 à 99,9% en poids d’huile(s) de base, de préférence encore de 80 à 99% en poids d’huile(s) de base, plus préférentiellement de 85 à 98% en poids d’huile(s) de base. 3. Use according to claim 1 or 2, in which the cooling composition comprises, relative to the total weight of the cooling composition, at least 70% by weight of base oil(s), preferably from 70 to 99 9% by weight of base oil(s), more preferably from 80 to 99% by weight of base oil(s), more preferably from 85 to 98% by weight of base oil(s) .
4. Utilisation selon la revendication 1 ou 2, dans laquelle la composition de refroidissement comprend 100% en poids d’huile(s) de base, par rapport au poids total de la composition de refroidissement. 4. Use according to claim 1 or 2, wherein the cooling composition comprises 100% by weight of base oil(s), based on the total weight of the cooling composition.
5. Utilisation selon l’une quelconque des revendications 1 à 4, dans laquelle la composition de refroidissement est mise en œuvre dans un dispositif de refroidissement d’une batterie comprenant au moins une boucle de circulation dans laquelle circule la composition de refroidissement. 5. Use according to any one of claims 1 to 4, in which the cooling composition is implemented in a device for cooling a battery comprising at least one circulation loop in which the cooling composition circulates.
6. Utilisation selon la revendication 5, dans laquelle la composition de refroidissement circule dans au moins un élément choisi parmi une pompe à huile, un échangeur fluide et un échangeur d’air.
6. Use according to claim 5, in which the cooling composition circulates in at least one element chosen from an oil pump, a fluid exchanger and an air exchanger.
7. Utilisation selon la revendication 5 ou 6, dans laquelle le dispositif de refroidissement comprend en outre au moins un réservoir de stockage de la composition de refroidissement. 7. Use according to claim 5 or 6, wherein the cooling device further comprises at least one storage tank for the cooling composition.
8. Utilisation selon l’une quelconque des revendications 1 à 7, dans laquelle la batterie est une batterie lithium-ion. 8. Use according to any one of claims 1 to 7, wherein the battery is a lithium-ion battery.
9. Utilisation selon l’une quelconque des revendications 1 à 8, pour refroidir la batterie. 9. Use according to any one of claims 1 to 8, to cool the battery.
10. Utilisation selon l’une quelconque des revendications 1 à 9, dans laquelle la batterie est mise en œuvre dans un système de propulsion d’un véhicule électrique ou hybride, de préférence un véhicule électrique.
10. Use according to any one of claims 1 to 9, wherein the battery is implemented in a propulsion system of an electric or hybrid vehicle, preferably an electric vehicle.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2105920A FR3123763B1 (en) | 2021-06-04 | 2021-06-04 | Battery cooling composition. |
| PCT/EP2022/065141 WO2022253992A1 (en) | 2021-06-04 | 2022-06-02 | Use of a cooling composition to protect a battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4348757A1 true EP4348757A1 (en) | 2024-04-10 |
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ID=77519229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22732117.1A Pending EP4348757A1 (en) | 2021-06-04 | 2022-06-02 | Use of a cooling composition to protect a battery |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP4348757A1 (en) |
| KR (1) | KR20240018442A (en) |
| CN (1) | CN117461188A (en) |
| FR (1) | FR3123763B1 (en) |
| WO (1) | WO2022253992A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120161472A1 (en) | 2010-12-22 | 2012-06-28 | Tesla Motors, Inc. | System for Absorbing and Distributing Side Impact Energy Utilizing an Integrated Battery Pack |
| KR101428383B1 (en) | 2013-04-26 | 2014-08-08 | 현대자동차주식회사 | Device for cooling battery module of vehicle |
| MX362538B (en) | 2013-09-04 | 2018-12-10 | Inst Tecnologico Estudios Superiores Monterrey | Lubricating oil for automotive and industrial applications, containing decorated graphene. |
| GB201811003D0 (en) * | 2018-07-04 | 2018-08-15 | Bp Plc | Multiple cooling circuit systems and methods for using them |
| WO2020132068A1 (en) * | 2018-12-20 | 2020-06-25 | Exxonmobil Research And Engineering Company | Low viscosity heat transfer fluids with increasing flash point and thermal conductivity |
| DK3984092T3 (en) * | 2019-06-12 | 2023-04-24 | Lubrizol Corp | ORGANIC HEAT TRANSFER SYSTEM, METHOD AND FLUID |
-
2021
- 2021-06-04 FR FR2105920A patent/FR3123763B1/en active Active
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2022
- 2022-06-02 KR KR1020237040664A patent/KR20240018442A/en unknown
- 2022-06-02 EP EP22732117.1A patent/EP4348757A1/en active Pending
- 2022-06-02 CN CN202280037302.9A patent/CN117461188A/en active Pending
- 2022-06-02 WO PCT/EP2022/065141 patent/WO2022253992A1/en active Application Filing
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| Publication number | Publication date |
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| WO2022253992A1 (en) | 2022-12-08 |
| CN117461188A (en) | 2024-01-26 |
| FR3123763A1 (en) | 2022-12-09 |
| KR20240018442A (en) | 2024-02-13 |
| FR3123763B1 (en) | 2024-01-05 |
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