Lithium-ion battery fire extinguishing composition and extinguisher comprising such composition

Abstract

Lithium-ion battery fire extinguishing composition and extinguisher comprising such a composition. The invention relates to a lithium-ion battery fire extinguishing composition comprising: - between 0.10% and 0.80% of a flame retardant, - between 0.10% and 0.23% of an amphoteric surfactant, - between 0.10% and 0.23% of an anionic surfactant, - between 0.10% and 0.23% of a foam stabilizer, - between 0.10% and 1.00% of a thermal stabilizer, - between 0.1% and 2% of an organic solvent selected from diols, glycols and glycol ethers, - Qsp of water. The invention also relates to a fire extinguisher (100) comprising such a composition, as well as a method for extinguishing a lithium-ion battery fire. Figure from the abstract: Fig. 2

Description

Title of the invention: Lithium-ion battery fire extinguishing composition and fire extinguisher comprising such a composition

[0001] The invention relates to a lithium-ion battery fire extinguishing composition and a fire extinguisher comprising such a composition.

[0002] In the context of the present invention, a lithium-ion accumulator is a device used for the electrochemical storage of energy and its restitution as needed. With reference to the English term "battery", the term "lithium-ion battery" is also used to designate this type of electric accumulator. It is an electrical generator consisting of two electrical conductors (namely the electrodes) in contact with an ionic conductor (the electrolyte) which may be in the form of a liquid, gel or solid. A lithium-ion accumulator consists of a set of cells which are connected together in a common housing. Each cell is a single source of electrical energy based on the conversion of chemical energy.

[0003] Indeed, the principle of the lithium-ion accumulator is based on the reversible exchange of the lithium ion between a cathode (generally a lithiated transition metal oxide such as cobalt or manganese dioxide) and an anode (generally graphite) during the charge and discharge cycles, and this with very good cycling performance. The electrolyte is aprotic (generally a dissolved lithium hexafluorophosphate salt) to passivate the anode and avoid degrading the highly reactive electrodes.

[0004] The lithium-ion accumulator has the following advantages in particular: - high energy density thanks to the properties of lithium, - good cyclability, - low self-discharge.

[0005] This is why the lithium-ion accumulator is widely used for everyday devices and vehicles (telephones, cars, bicycles, electrical tools) and in systems using renewable energies (solar, wind).

[0006] However, this lithium technology has the major disadvantage that the contents of the lithium-ion battery cells risk catching fire in the event of overcharging, heating or mechanical damage. A chemical reaction known as "thermal runaway" can occur within one of the cells and spread to adjacent cells. This releases a huge amount of energy in a very short time. This thermal runaway is accompanied by a sharp increase in temperature and pressure within the cell, as well as the generation of intense flames that spread throughout the cell pack until it has completely burned. In addition, this can also ignite combustible materials near the lithium-ion battery.

[0007] Therefore, it is necessary to have fire extinguishers comprising a fire extinguishing composition which is perfectly adapted to this type of very dangerous situation of lithium-ion battery ignition.

[0008] Fire extinguishing compositions generally contain flame retardants in association with surfactants (which act as foaming agents), solvents, water, and other additives which provide the desired mechanical and chemical properties to the foam formed when said extinguishing composition is used with a fire extinguisher. Fire extinguishing compositions are constantly being improved in order to optimize their foaming characteristics, and to obtain a fire extinguishing process which is rapid, effective, and finally particularly adapted to the specific fires for which they are intended.

[0009] In the context of the present invention, a fire extinguisher is a portable device used to extinguish or control a small or medium-sized fire. A fire extinguisher generally comprises a cylindrical container comprising a fire extinguishing composition which is pressurized by means of a propellant gas so as to be discharged onto the fire which is desired to be extinguished.

[0010] The inventors of the present invention have developed a fire extinguishing composition which is particularly suited to the specificities of fires started by lithium-ion accumulators and which have been detailed above.

[0011] This is why the invention relates to a lithium-ion battery fire extinguishing composition which is characterized in that it comprises, in mass percentages expressed relative to the total mass of said composition: - between 0.10% and 0.80%, preferably between 0.30% and 0.70%, of at least one flame retardant, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one amphoteric surfactant, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one anionic surfactant, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one foam stabilizer, - between 0.10% and 1.00%, preferably between 0.15% and 0.70%, of at least one thermal stabilizer, - between 0.1% and 2%, preferably between 0.5% and 1%, of at least one organic solvent chosen from diols, glycols and glycol ethers, - Qsp of water.

[0012] "Qsp" is the acronym for "Quantity sufficient for" to mean that the mass percentage of water in the fire extinguishing composition is such that, added to the percentages of all the other constituents of said fire extinguishing composition, a total of 100% is obtained.

[0013] In the context of the present invention, the following terms are understood to mean: - “fire retardant” means an agent intended to prevent or slow the development of a fire; - “amphoteric surfactant”, a surfactant comprising cationic and anionic functions, - “anionic surfactant”, a surfactant comprising an anionic function.

[0014] In a highly advantageous manner, the fire extinguishing composition according to the invention is free of any fluorinated compound. This means that in these embodiments, the amphoteric and anionic surfactant(s) do not contain fluorine in their chemical structure. Indeed, fluorinated surfactants which were used for a long time due to their good properties are currently excluded from fire extinguishing compositions for health and environmental reasons.

[0015] The inventors of the present invention have discovered, quite surprisingly, that the combination of at least one flame retardant with at least one amphoteric surfactant and at least one anionic surfactant in the amounts as detailed above makes it possible to obtain a fire extinguishing composition that is particularly suitable for lithium-ion battery fires. Indeed, this fire extinguishing composition has the following advantages: when it is sprayed onto the flames of the fire with a fire extinguisher at an initial projection pressure of approximately 10 to 12 bars and with a high flow rate, said composition has, in a first stage (approximately the first 10 seconds), a wetting effect which makes it possible to act in a targeted manner at the heart of the burning cell by very rapidly reducing its temperature and extinguishing the flames and preventing their propagation.Then, in a second step, with a lowering of the projection pressure, said composition has a foaming effect whose volume increases over time so as to "coat" all the cells of the lithium-ion accumulator with said foam. This has the effect of cooling all the cells of the lithium-ion accumulator by capturing the heat produced, and thus lowering the temperature and avoiding any risk of re-ignition or explosion of one of the cells.

[0016] Indeed, after having initially contained the flames, there remains heat within the lithium-ion accumulator which must be dissipated as quickly as possible to avoid any re-ignition or explosion. As the extinguishing composition according to the invention is projected, the foam which forms becomes increasingly bulky and thick. It surrounds all the cells of the lithium-ion battery (including the one that started the fire) so as to also retain the water that continues to be sprayed by the fire extinguisher so that this water cools all the cells of the lithium-ion battery.

[0017] In addition, the foam obtained with the fire extinguishing composition remains stable when it is sprayed onto the burning lithium-ion battery and it has a high expansion rate.

[0018] The expansion rate is the ratio between the volume of the foam produced by the fire extinguishing composition according to the invention and the volume of said fire extinguishing composition. The higher the expansion rate, the lighter the foam and the greater its volume.

[0019] The inventors of the present invention have thus discovered, quite surprisingly, that a fire extinguishing composition comprising very small amounts of flame retardant (i.e. between 0.10% and 0.80%, preferably between 0.30% and 0.70%) in combination with very small amounts of anionic and amphoteric surfactants (i.e. between 0.10% and 0.23%, preferably between 0.15% and 0.21%), compared with the fire extinguishing compositions known from the state of the art, was perfectly suitable for extinguishing lithium-ion battery fires as explained above.

[0020] Furthermore, the organic solvent in the quantity detailed above allows the formation of a high volume of foam and in which the flame retardants are diffused homogeneously.

[0021] The flame retardant agent that the fire extinguishing composition according to the invention comprises is advantageously chosen from the group consisting of ammonium phosphates, phosphate esters, halogenated phosphates, phosphonates, red phosphorus, calcium silicate, sodium silicate, aluminum trihydroxide, magnesium dihydroxide, polybrominated diphenyl ethers, tetrabromobisphenol A, hexabromocyclododecane and bromophenols, taken alone or as a mixture thereof.

[0022] Preferably, the flame retardant is chosen from ammonium phosphates. Most preferably, the flame retardant is diammonium phosphate and / or ammonium dihydrogen phosphate.

[0023] The amphoteric surfactant may advantageously be chosen from the group consisting of betaines, sultaines, alkylamphoacetates, amphodiacetates, alkyllamphopropionates, alkyliminodipropionates, amphodipropionates, aliphatic quaternary ammonium compounds, aliphatic quaternary phosphonium compounds and aliphatic quaternary sulfonium compounds, taken alone or as a mixture thereof.

[0024] In a completely advantageous manner, the amphoteric surfactant can be chosen from the group consisting of betaines, sultaines, alkylamphoacetates, amphodiacetates, alkylamphopropionates, alkyliminodipropionates and amphodipropionates, taken alone or as a mixture thereof.

[0025] Preferably, the amphoteric surfactant is a betaine and / or an alkylampho-propionate.

[0026] When the amphoteric surfactant is a betaine, it may be chosen from the group consisting of betaines, alkyl betaines, alkylamido betaines and sulfo-betaines.

[0027] For example, with respect to alkyl betaines, these may be coco dimethyl carboxymethyl betaine, cocobetaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine.

[0028] For example, with regard to alkyl amidopropyl betaines, these may be cocoamidopropyl betaine, lauryl amidopropyl betaine, oleamidopropyl betaine, erucic amidopropyl betaine.

[0029] For example, as regards sulfobetaines, it may be coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine.

[0030] The amphoteric surfactant may be a compound selected from aliphatic quaternary ammonium, quaternary phosphonium or quaternary sulfonium compounds. These may be 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-l-carboxylate, 5-[S-3-hydroxypropyl-5-hexadecylsulfonio]-3-hydroxypentane- 1-sulfate, 3-[P,P-diethyl-P-3,6,9-trioxatetradecoxylphosphonio]-2-hydroxy-propane-l-phosphate, 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-1-phosphonate, 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate, 4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane-l-carboxylate, 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-l-phosphate, 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate or 5-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane- 1-sulfate.

[0031] Preferably, the amphoteric surfactant is chosen from the group consisting of coco dimethyl carboxymethyl betaine, oleyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, lauryl amidopropyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine and al- kylamphopropionates, taken alone or in a mixture of these.

[0032] The anionic surfactant may advantageously be selected from the group consisting of alkyl sulfates, alkyl ether sulfates, alkyl ether sulfonates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, ammonium alcohol sulfates, alpha-olefin sulfonates, beta alkoxy alkane sulfonates, alkylauryl sulfonates, alkyl monoglyceride sulfates, alkyl monoglyceride sulfonates, alkyl carbonates, alkyl ether carboxylates, fatty acids, fatty alcohol sulfates, sulfosuccinates, sar-cosinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, polyoxyethylene fatty acid amides, isethionates and anionic derivatives of alkyl polyglucosides, taken alone or in mixtures thereof.

[0033] Preferably, the anionic surfactant is selected from C8-C18 alkyl sulfates, C8-C18 fatty acid salts, C8-C18 alkyl ether sulfates having one or two moles of ethoxylation, C8-C18 alkamine oxides, C8-C18 alkyl sarcosinates, C8-C18 sulfoacetates, C8-C18 sulfosuccinates, C8-C18 alkyl diphenyl oxide disulfonates, C8-C18 alkyl carbonates, C8-C18 alpha-olefin sulfonates and methyl ester sulfonates, taken alone or as a mixture thereof.

[0034] Advantageously, the anionic surfactant is selected from lauryl sulfates, octyl sulfates, 2-ethylhexyl sulfates, lauramine oxide, decyl sulfates, tridecyl sulfates, triethanol ammonium alkyl sulfate, cocoates, lauroyl sarcosinates, lauryl sulfosuccinates, C10 linear diphenyl oxide disulfonates, lauryl sulfosuccinates, lauryl ether sulfates, myristyl sulfates, oleates, stearates, tallates, ricinoleates and cetyl sulfates, taken alone or as a mixture thereof.

[0035] The anionic surfactant may also be chosen from alkyl sulfonates, alkylaryl sulfonates, alkylated diphenyl oxide disulfonates, alkylated naphthalene sulfonates, isethionates, alkylaryl sulfonic acids, secondary alkane sulfonates, alkoxylate carboxylates, sarcosinates, taurate, acyl amino acids, alkanoic esters, phosphate esters, sulfuric acid esters, taken alone or as a mixture thereof.

[0036] Preferably, the anionic surfactant is selected from sodium lauryl glucoside carboxylate, disodium coco-glucoside citrate, sodium coco-glucoside tartrate, disodium coco-glucoside sulfosuccinate, sodium cocoglucoside hydroxypropylsulfonate, sodium decylglucoside hydroxypropylsulfonate, sodium laurylglucoside hydroxypropylsulfonate, crosslinked polymers of sodium coco-glucoside-hydroxypropylsulfonate, crosslinked polymers of sodium decyl-glucoside-hydroxypropylsulfonate, crosslinked polymers of lauryl- sodium glucoside-hydroxypropylsulfonate, taken alone or in a mixture of these.

[0037] Most preferably, the anionic surfactant is chosen from the group consisting of alkylated naphthalene sulfonates, sodium coco-glucoside hydroxypropylsulfonate, crosslinked polymers of sodium cocoglucoside-hydroxypropylsulfonate and crosslinked polymers of sodium laurylglucoside-hydroxypropylsulfonate, taken alone or as a mixture thereof.

[0038] The organic solvent may be selected from the group consisting of ethylene glycol, propylene glycol, butyl-di-glycol, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol, n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, dipropylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether, ethylene glycol hexyl ether, hexyl ether diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol, monobutyl ether,ethylene glycol monobenzyl ether, diethylene glycol phenyl ether, ethylene glycol phenyl ether, poly(oxy-1,2-ethanediyl), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-butyl ether, ethylene glycol n-butyric ether, dipropylene glycol methyl ether, taken alone or as a mixture thereof.

[0039] Most preferably, the organic solvent is chosen from the group consisting of ethylene glycol, propylene glycol and dipropylene glycol n-propyl ether, taken alone or as a mixture thereof.

[0040] The fire extinguishing composition according to the invention comprises at least one foam stabilizer. This makes it possible to improve the stability of the foam and therefore to prolong the fire extinguishing activity of said composition.

[0041] Foam stabilizers are perfectly known to those skilled in the art. The at least one foam stabilizer may be chosen from aliphatic fatty alcohols and amides containing 8 to 25 carbon atoms, polyethylene glycol and polypropylene glycol. For example, with regard to fatty alcohols, it may be lauryl, myristyl or cetyl alcohol.

[0042] The fire extinguishing composition according to the invention comprises at least one thermal stabilizer. The thermal stabilizer makes it possible to improve the stability of the foam obtained from the extinguishing composition according to the invention under fire conditions which can reach extremely high temperatures because which can be between approximately 75°C and approximately 500°C.

[0043] The heat stabilizer may be selected from the group consisting of ammonium phosphate, ester phosphates, sodium citrate, sucrose, maltose, dextrose, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium sulfate, sodium orthophosphate, taken alone or as a mixture thereof. Preferably, the heat stabilizer is selected from sucrose, maltose and dextrose, taken alone or as a mixture thereof.

[0044] In one embodiment of the invention, the fire extinguishing composition comprises, in mass percentages expressed relative to the total mass of said composition: - between 0.10% and 0.80%, preferably between 0.30% and 0.70%, of at least one flame retardant agent chosen from ammonium phosphates, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one amphoteric surfactant chosen from betaines and / or alkylamphopropionates, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one anionic surfactant chosen from alkyl sulfates, alkyl ether sulfates, alkyl ether sulfonates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, ammonium alcohol sulfates, alpha-olefin sulfonates, beta alkoxy alkane sulfonates, alkylauryl sulfonates, alkyl monoglyceride sulfates, alkyl monoglyceride sulfonates, alkyl carbonates, alkyl ether carboxylates, fatty acids, fatty alcohol sulfates, sulfosuccinates, sarcosinates, octoxynol or nonoxynol phosphates, taurates, fatty acids, polyoxyethylene fatty acid amides, isethionates and anionic derivatives of alkyl polyglucosides, taken alone or in mixtures thereof, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one foam stabilizer chosen from aliphatic alcohols and fatty amides containing 8 to 25 carbon atoms, polyethylene glycol and polypropylene glycol, taken alone or as a mixture thereof, - between 0.10% and 1.00%, preferably between 0.15% and 0.70%, of at least one heat stabilizer chosen from ammonium phosphate, ester phosphates, sodium citrate, sucrose, maltose, dextrose, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium sulfate and sodium orthophosphate, taken alone or as a mixture thereof, - between 0.1% and 2%, preferably between 0.5% and 1%, of at least one organic solvent chosen from ethylene glycol, propylene glycol, butyl-di-glycol, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol, n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, ether dipropylene glycol phenyl ether, dipropylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether, ethylene glycol hexyl ether, diethylene glycol hexyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol, monobutyl ether, ethylene glycol monobenzyl ether, diethylene glycol phenyl ether, ethylene glycol phenyl ether, poly(oxy-1,2-ethanediyl), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-butyl ether, ethylene glycol n-butyl ether and dipropylene glycol methyl ether, taken alone or as a mixture thereof,- Qsp of water. ,

[0045] In one embodiment of the invention, the fire extinguishing composition comprises, in mass percentages expressed relative to the total mass of said composition: - between 0.10% and 0.80%, preferably between 0.30% and 0.70%, of at least one flame retardant agent chosen from diammonium phosphate and / or ammonium dihydrogen phosphate, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one amphoteric surfactant chosen from the group consisting of coco dimethyl carboxymethyl betaine, oleyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, lauryl amidopropyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine and alkylamphopropionates, taken alone or as a mixture thereof, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one anionic surfactant chosen from the group consisting of alkylated naphthalene sulfonates, sodium cocoglucoside hydroxypropylsulfonate, crosslinked polymers of sodium cocoglucoside-hydroxypropylsulfonate and crosslinked polymers of sodium laurylglucoside-hydroxypropylsulfonate, taken alone or as a mixture thereof, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one foam stabilizer chosen from lauryl, myristic, cetyl alcohol, polyethylene glycol and polypropylene glycol, taken alone or as a mixture thereof, - between 0.10% and 1.00%, preferably between 0.15% and 0.70%, of at least one heat stabilizer chosen from sucrose, maltose and dextrose, taken alone or as a mixture thereof, - between 0.1% and 2%, preferably between 0.5% and 1%, of at least one organic solvent chosen from ethylene glycol, propylene glycol and di-n-propyl ether propylene glycol, taken alone or in a mixture of these. - Qsp of water.

[0046] The fire extinguishing composition according to the invention is used with a fire extinguisher to extinguish a lithium-ion battery fire.

[0047] This is why the invention relates to a fire extinguisher which is characterized in that it comprises at least one fire extinguishing composition according to the invention and as described above.

[0048] Furthermore, the inventors of the present invention have discovered, quite surprisingly, that the extinguishing composition according to the invention as described above is particularly effective in extinguishing a lithium-ion battery fire when used in association with a fire extinguisher having specific technical characteristics which are described below.

[0049] This is why, advantageously, the fire extinguisher comprises: - a sealed tank extending along an axis and containing the fire extinguishing composition according to the invention as described above, said tank is configured to comprise an expansion chamber formed by a part of the tank not filled with said fire extinguishing composition, - a flushing bottle, sealed and containing a pressurized propellant gas, for use as a propellant for the fire extinguishing composition, the flushing bottle being housed inside the tank and having, for the propellant gas, an outlet fluidically connected to the inside of the tank, said fire extinguisher is characterized in that it further comprises: - a mixing tube having a 1st end and a 2nd end, the 1st end being fluidically connected to the outlet of the flush bottle and the 2nd end being closed, said mixing tube comprises at least one lateral orifice relative to the axis and which is configured to release the propellant gas into the expansion chamber of said tank.

[0050] By "a part of the tank not filled with the fire extinguishing composition" is meant a part of the tank delimiting a 1st volume of the tank not occupied by the fire extinguishing composition from a 2nd volume of the tank occupied by said fire extinguishing composition. It will be understood that the delimitation between the 1st volume and the 2nd volume depends on the level of the fire extinguishing composition contained in the tank movable in the tank depending on the orientation given to the tank relative to a vertical axis relative to the ground.

[0051] When the pressurized propellant gas is released, it is injected into the expansion chamber of the tank so as to pressurize it so that the pressure contained in this expansion chamber in turn pressurizes the fire extinguishing composition, thus promoting its rise through a riser tube which can include the fire extinguisher and thus its outlet from the fire extinguisher. Thus, in one embodiment of the invention, the fire extinguisher may thus comprise a riser tube and a flexible lance tube.

[0052] This riser tube is fluidically connected to this flexible lance tube which is provided with sealed closure means and the opening of which can be controlled and adjusted to release the fire extinguishing composition according to the invention. Preferably, one of the ends of the riser tube is close to the bottom of the tank. This facilitates the exit of all, or almost all, of the fire extinguishing composition when using the fire extinguisher. The riser tube advantageously has a length of 575 mm.

[0053] The at least one side orifice allows the propellant gas to arrive in the expansion chamber. Thus, it does not diffuse into the fire extinguishing composition. This configuration of the mixing tube prevents the propellant gas from depleting the foaming power of the fire extinguisher.

[0054] It will be understood that, for the mixing tube, a lateral orifice relative to the axis of the reservoir, is formed laterally on this tube, that is to say on the side wall of this tube in any direction along a secondary axis having a different orientation from the axis of the reservoir, the secondary axis being intersecting the axis of the reservoir or not intersecting the axis of the reservoir.

[0055] Optionally, the at least one lateral orifice is radial relative to the axis of the reservoir.

[0056] In one embodiment of the invention, said mixing tube comprises two lateral orifices (more preferably radial) relative to the axis of the tank.

[0057] The at least one lateral orifice may have a diameter of between 0.5 mm and 2.5 mm, preferably between 1 mm and 2 mm, even more preferably equal to 2 mm.

[0058] In a preferred embodiment of the invention, the mixing tube comprises 2 lateral orifices (more preferably radial) relative to the axis of the tank. These 2 lateral orifices (more preferably radial) advantageously have a diameter equal to 2 mm.

[0059] Preferably, the at least one lateral orifice which is closest to the 1st end of the mixing tube is located at a distance of approximately 2 cm from said 1st end.

[0060] According to one embodiment of the invention, the flushing bottle internally comprises a sealed propellant gas rise tube, connected in a sealed manner to the outlet of the flushing bottle and fluidically connected in the flushing bottle. Thus, after striking a seal of the flushing bottle, the entire expulsion of the propellant gas is facilitated since it can only leave the flushing bottle by rising in this mixing tube.

[0061] The propellant gas may be selected from the group consisting of nitrogen, argon and carbon dioxide, taken alone or as a mixture thereof. Preferably, the propellant gas is carbon dioxide.

[0062] As explained above, the fire extinguisher comprises a riser tube allowing the fire extinguishing composition to exit the fire extinguisher.

[0063] This riser tube opens onto a 1st end of an outlet duct which is itself connected in a sealed manner at its 2nd end to a flexible and sealed lance tube (for example with a length of 700 mm). The 2nd end of the outlet duct very advantageously has a diameter of 11 mm. This allows an operating time of the fire extinguisher of approximately 90 seconds; which is perfectly suitable for extinguishing a lithium-ion battery fire.

[0064] The flexible lance tube is provided with sealed closure means and controlled and regulated opening, by action of the operator on a handle, for example automatically returned to a state corresponding to the sealed closure of said flexible tube. These closure means are advantageously connected to a diffusion system configured for spraying the fire extinguishing composition. In one embodiment of the invention, the fire extinguisher comprises a diffusion system.

[0065] Preferably, the diffusion system is a Venturi effect diffuser. This has the advantage of aerating the fire extinguishing composition according to the invention at the outlet of the flexible and sealed lance tube and thus it transforms into foam when the spray pressure of said fire extinguishing composition is lowered. For example, without being limited thereto, the diffusion system may be or advantageously comprise an extinguishing nozzle as described in patent application BE 1028003 AL

[0066] The invention may further comprise one of the following features taken alone or in combination: - the mixing tube is not immersed in the fire extinguishing composition, - the length of the mixing tube may be between 50 mm and 540 mm, preferably equal to 125 mm, - the total height of the tank may be between 400 mm and 600 mm, preferably between 428 mm and 580 mm, - the volume of fire extinguishing composition that the tank can contain is between 6 L and 9 L, preferably 9 L, - the volume of the expansion chamber can be between 1.5L and 1.8L, preferably 1.6L, - the internal volume of the tank can be between 7.75L and 12L, preferably 10.6 L, - the mixing tube has an internal diameter of between 3 mm and 10 mm, preferably between 6 mm and 7 mm, even more preferably equal to 5 mm, - a watertight sealing cap at the outlet of the flushing bottle for the propellant gas, - means of controlling the percussion of the cover.

[0067] In one embodiment of the invention, the mixing tube has an inner diameter of between 3 mm and 10 mm and a length of between 50 mm and 540 mm.

[0068] The length of the mixing tube as described above, preferably equal to 125 mm, is particularly suitable so that in association with the at least one lateral orifice, the propellant gas diffuses correctly into the expansion chamber in order to pressurize the fire extinguishing composition according to the invention.

[0069] In one embodiment of the invention, the fire extinguisher may be configured such that the pressure of the fire extinguishing composition at the outlet of the extinguisher and which is sprayed into the air in order to extinguish the lithium-ion battery fire changes as follows over time: - initial time (“t=0”): at the moment the flush bottle seal is struck, the pressure is between 12 bars and 14 bars, the fire extinguishing composition is wetting, i.e. still essentially in liquid form. This allows the flames to be extinguished. - between the initial time and 5 seconds after the initial time, the pressure has decreased to approximately 8 bars. The fire extinguishing composition begins to foam. It begins to drip slowly around the lithium-ion battery. - between 5 seconds and 20 seconds after the initial time, the pressure has decreased to approximately 5 bars. The fire extinguishing composition is mainly in the form of foam. - between 30 seconds and 60 seconds after the initial time, the pressure has decreased further to approximately 4 bars. The fire extinguishing composition is mainly in the form of foam. - between 60 seconds and 90 seconds after the initial time, the pressure has decreased to approximately 0 bar. The fire extinguishing composition is mainly in the form of foam.

[0070] It is important to emphasize that when the fire extinguishing composition is in the form of foam, it covers the lithium-ion battery and slowly falls along the walls thereof; which forms a heat barrier and thus makes it possible to reduce the temperature of the burnt lithium-ion battery and thus extinguishing the fire perfectly.

[0071] The invention also relates to a method for extinguishing a fire in a lithium-ion accumulator which is characterized in that a fire extinguishing composition according to the invention as described above is sprayed with a fire extinguisher according to the invention as described above onto a burning lithium-ion accumulator.

[0072] Other characteristics and advantages of a fire extinguisher according to any one of the aspects of the invention will emerge from the description below, relating to a non-limiting example of its embodiment.

[0073] [Fig-1] represents a sectional view of the extinguisher according to the invention in the assembled state, equipped with a lance hose, a trigger and a diffuser, this to particularly illustrate a riser tube contained in its tank.

[0074] [Fig.2] represents another sectional view of the fire extinguisher according to the invention in the state assembled, without the lance hose, trigger and diffuser, this is to particularly illustrate a mixing tube contained in the tank.

[0075] [Fig.3] represents an enlargement of [Fig.2] illustrating in more detail a configuration of the mixing tube.

[0076] [Fig.4] represents a sectional view of a flushing bottle included in the tank and containing the propellant gas.

[0077] [Fig.5] represents a partially exploded view of the extinguisher where the interior of the tank has been partially shown.

[0078] [Fig.6] represents a perspective view of an example of a diffusion system.

[0079] With reference to the figures, a sectional view of the fire extinguisher 100 according to the invention is shown. The fire extinguisher comprises a reservoir 120 and a cover 180. The reservoir 120 has a general shape of revolution around an axis A1 which, in a determined orientation of use of the fire extinguisher 100, is vertical relative to a horizontal plane, as illustrated in the figures or forms a few degrees of angle of inclination relative to the vertical. This determined orientation of use of the fire extinguisher 100 will serve as a reference for the remainder of the description.

[0080] By "vertical" is meant the direction of the gravity vector; and by "horizontal plane" is meant a plane perpendicular to this direction of the gravity vector.

[0081] The tank 120 has a side wall 121, for example cylindrical of revolution around the axis A1, a bottom wall 122, for example convex downwards, to which this side wall 121 is connected in a lower zone of the tank 120, and a top wall 123 to which the side wall 120 is connected in an upper zone of the tank 120. These walls 120-123 are sealed and connected to each other in a gas- and liquid-tight manner so as to contain a fire extinguishing composition according to the invention 200 which fills the tank 120, for example example over most of its height, the remainder of the tank 120 being filled with air at atmospheric pressure, the air being located in the upper zone of the tank 120. Said remainder of the tank 120 forms an expansion chamber 120' in the tank 120.

[0082] The term “top” is defined relative to the axis Al as towards the top wall 123 of the reservoir 120, while the term “bottom” is defined relative to the axis Al as towards the bottom wall 122 of the reservoir 120.

[0083] The top wall 123 is pierced, from side to side, with an orifice 123A for filling with fire extinguishing composition 200. This orifice 123A is advantageously delimited by an edge 123B of the top wall 123, which edge 123B is annular of revolution around the axis AL. The cover 180 is attached, for example in a removable manner, to the reservoir 120, to seal the orifice 123A in a sealed manner, and, as better shown in [Fig. 5], comprises for this purpose a flat wall 181 having the general shape of a disc of revolution around the axis Al, which flat wall 181 has towards the bottom an annular groove, of revolution around the axis Al, suitable for receiving the edge 123B of the orifice 123A and for being applied in a sealed manner to this edge 123B by means of of a seal not shown, when the cover 180 is fixed on the tank 120.This fixing is carried out for example, in a manner known per se, by bolting 124, preserving the sealing of the tank 120 by the flat wall 181 of the cover 180, on the top wall 123 around the orifice 123A of the tank 120.

[0084] The flat wall 181 thus has, downwards, a flat lower face 181A, perpendicular to the axis A1, in which the groove is hollowed out. In the direction of distance from the axis A1, the lower face 181A connects to a non-referenced edge of the flat wall 181, which has, for example, a generally cylindrical shape of revolution around the axis A1 and connects the lower face 181A of the flat wall 181 to an upper face 181B of the flat wall 181. This upper face 181B, located outside the reservoir 120 and consequently exposed to the ambient air, is flat and perpendicular to the axis A1 like the face 181A.

[0085] On the upper face 181B, there projects upwards, along the axis A1, a boss 182 advantageously made in one piece with the flat wall 181 and pierced, on one side of the axis A1, with a conduit 183 for the outlet of the fire extinguishing composition 200 contained in the reservoir 120, which conduit 183 has for this purpose an opening 183A opening into the lower face 181A of the flat wall 181 and an opening 183B in the boss 182.

[0086] The extinguisher 100 further comprises control means 140 for striking a cover 134 of the flushing bottle 130.

[0087] The mouth 183A extends inside the tank 120, by a straight and sealed riser tube 160, having in the lower zone of the tank 120 a lower end 160A open downwards, at an angle, and in the upper zone of the reservoir 120 an upper end 160B open upwards and connected in a sealed manner, around the mouth 183A, to the edge of the latter, for example by coaxial fitting of this upper end 160B into the mouth 183A or by coaxial screwing of this upper end 160B into the mouth 183A, suitably tapped for this purpose. The lower end 160A of the riser tube 160 is immersed in the fire extinguishing composition 200 for a wide range of orientations of the axis A1 relative to the vertical and even if there remains only a bottom of fire extinguishing composition 200 in the tank 120, at the end of the use of the extinguisher 100, and the riser tube 160 can thus ensure even under such conditions the rise of the fire extinguishing composition 200 to the mouth 183A and the outlet 183B of the conduit 183.

[0088] The conduit 183 is advantageously connected, in a sealed manner, to a flexible and sealed lance tube 190 provided with sealed closure means 191 and controlled and regulated opening, by action of the operator on a handle 191 A, for example automatically returned to a state corresponding to the sealed closure of the tube 190, which closure means 191 are connected to a diffusion system 1 (or in other words an extinguishing nozzle 1), of the fire extinguishing composition 200 to be sprayed into the ambient air.

[0089] Without being limited thereto, the diffusion system 1 may be or advantageously comprise an extinguishing nozzle 1 as described in patent application BE 1028003 AL Such an extinguishing nozzle 1 is shown in [Fig.6], it comprises a mixing chamber 2, a ventilation chamber 3 and a foaming chamber 4, wherein said ventilation chamber 3 is coupled to said mixing chamber 2, and comprises a first hollow cylindrical body 5 comprising 4 air inlet holes 6, said air inlet holes 6 are arranged on the circumference and are directed into the first hollow cylindrical body 5. The foaming chamber 4 comprises a second hollow cylindrical body 7 having an axial length L and an inner diameter d, which foaming chamber 4 is coupled to said ventilation chamber 3.The ventilation chamber 3 and / or the foaming chamber 4 comprise a lattice (not visible), wherein said lattice is oriented in the radial plane of the inner cross-section of the ventilation chamber 3 and / or the foaming chamber 4, and in that the ratio between the axial length and the inner diameter L:d of the foaming chamber 4 is between 4:5 and 9:5.

[0090] In a position offset from that of the conduit 183, the cover 180 is hollowed out with another conduit 184 having both a mouth 184A and an outlet 184B in the lower face 181A of the flat wall 181.

[0091] More precisely, from its mouth 184A to its outlet 184B, the conduit 184 has a first section 184C connected to the mouth 184A, a second section 184D, a third section 184E connected to the outlet 184B, and the second section 184D connecting the first section 184C to the third section 184E.

[0092] The first section 184C extends coaxially upwards, beyond the connection of the second section 184D, by a bore 184F opening into the open air in the upper face 181B of the flat wall 181. The bore 184F defines by its connection with the first section 184C an annular shoulder. The bore 184F receives and guides in coaxial sliding a rod 141 of the percussion control means 140, which is sealed with respect to the bore 184F by a sealing gasket thus preserving the seal between the conduit 184 and the ambient air. Above the upper face 181B of the flat wall 181, this rod 141 has a convex upper end 141A, for example hemispherical, around which the boss 182 forms a yoke.

[0093] The fire extinguisher comprises a handle 142. The handle 142 may be for carrying and / or, as will appear later, may be for activating the fire extinguisher 100 by percussion. This handle 142 extends in a cantilevered manner, opposite the conduit 183 relative to the axis A1, and the handle 142 is for example pivotally mounted. As long as it is not desired to put the extinguisher 100 into service, the handle 142 is held, by a removable pin 143 perpendicular to the axis A1 and bearing downwards on the flat wall 181, in an upper limit position illustrated in figures 1 and 2, but when an operator wishes to put the extinguisher 100 into service, he removes the pin 143, which frees the handle 142 from tilting downwards relative to the boss 182.

[0094] The handle 142 has, integrally, above the convex upper end 141A of the rod 141, a bearing surface 142A allowing, when the handle 142 is tilted by the operator, to apply to the rod 141, by means of its convex upper end 141A, a force forcing the rod 141 to slide downwards inside the bore 184F of the flat wall 181, from a high position which is illustrated in the figures and which it occupies. In this high position, the bearing surface 142A is slightly spaced, upwards, from the convex upper end 141A of the rod 141 itself occupying its high position but, when the operator tilts the handle 142 downwards after having unpinned it, the latter comes to abut downwards by the bearing surface 142A on the upper end 141A of the rod 141 then causes a sliding movement of the latter downwards inside the bore 184F of the flat wall 181.

[0095] Inside the first section 184C of the conduit 184, the rod 141 has a widened lower end, in the form of a collar 141B, this collar 141B is shaped with respect to the connecting shoulder between the bore 184F and the first section 184C.

[0096] The rod 141 is extended, integrally downwards, by a hollow needle 141C having an unreferenced external peripheral face with a diameter smaller than the respective diameters of the collar 141B and the first section 184C of the conduit 184.

[0097] The rod 141 and the hollow needle 141C, which may be made in a single piece, constitute a striker, actuated by the handle 142, to controllably release a pressurized propellant gas 300 which is carbon dioxide and which is intended to expel the fire extinguishing composition 200 from the reservoir 120.

[0098] This propellant gas 300 is contained in a flushing bottle 130 housed inside the tank 120 and connected in a sealed and integral manner, the flushing bottle 130 is preferably removable, at the mouth 184A of the first section 184C of the conduit 184, mounted for example by tapping.

[0099] The flushing bottle 130 may have a shape of revolution around an axis A2, optionally parallel to the axis AL. The flushing bottle 130 is delimited by a side wall 131, cylindrical of revolution around the axis A2, with an outside diameter smaller, for example much smaller, than the inside diameter of the side wall 121 of the tank 120 so as to allow its introduction, and / or respectively its extraction, through the orifice 123A of the tank 120, together with the riser tube 160, when the cover 180 is placed on the tank 120 and / or respectively when this cover 180 is removed for maintenance or for refilling the extinguisher 100 used.Downwards, the wall 131 connects to a bottom wall 132, defining a lower zone of the flushing bottle 130 and having for example a downward convexity, that is to say towards the bottom wall 122 of the tank 120 whereas, upwards, it connects to a top wall 133 defining an upper zone of the flushing bottle 130 with a convex shape towards the cover 180; the bottom walls 132 and top walls 133 are for example hemispherical or the bottom wall 132 is as shown in [Fig.4].

[0100] The term "top" is defined relative to the axis A2 as towards the top wall 133 of the flushing bottle 130, while the term "bottom" is defined relative to the axis A2 as towards the bottom wall 132 of the flushing bottle 130.

[0101] The walls of the flushing bottle 130 are sealed and mutually connected in a sealed manner, except that the top wall 133 is connected to a tubular neck 133A, of revolution around the axis A2, projecting from its connection with the top wall 133, and opened by an outlet orifice 133B of the propellant gas 300.

[0102] When the extinguisher 100 is not in use, the outlet orifice 133B is sealed by a sealed cover 134 of the flushing bottle 130, fixed in a sealed but preferably removable manner to the flushing bottle 130 around the outlet orifice 133B.

[0103] The seal 134 is chosen so that it can be easily perforated by the needle 141C, on the one hand, but the seal 134 and its attachment are chosen so as to withstand the overpressure prevailing inside the flushing bottle 130 in comparison with the interior of the tank 120 before perforation under normal storage conditions of the extinguisher, on the other hand. The seal 134 is preferably turned to break as a priority, that is to say preferentially at the flushing bottle 130, in the event of abnormally high overpressure therein, in order to avoid an explosion of the flushing bottle 130 in such a case.

[0104] Once the seal 134 is perforated, the propellant gas 300 escapes from the flush bottle 130 through the outlet orifice 133B towards the conduit 184 towards the space located inside the tank 120 to pressurize the fire extinguishing composition 200.

[0105] This pressurization of the fire extinguishing composition 200 is facilitated by the implementation of a mixing tube 150 sealed at the outlet 184B of the conduit 184 connecting in a sealed manner, for example by fitting, into this conduit 184.

[0106] The rectilinear, sealed mixing tube 150 has a first end called the upper end 150A, open, directly attached to the outlet 184B and a second end called the lower end 150B, which is closed and which is preferably not immersed in the fire extinguishing composition 200.

[0107] The mixing tube 150 has two lateral orifices 153A relative to the axis A1 to release the propellant gas 300 contained in the flushing bottle 130 directly into the expansion chamber 120' of the tank 120.

[0108] The lateral orifices 153A are radial with respect to the axis Al, but as explained above, they could take any orientation along a secondary axis intersecting the axis AL

[0109] According to an embodiment not shown, the two orifices 153A pass right through the wall of the mixing tube 150 in the same direction.

[0110] Furthermore, total expulsion of the propellant gas 300 from the flushing bottle 130 is ensured by providing inside the flushing bottle 130 a sealed dip tube 135 having an upper end 135A connected in a sealed manner to the neck 133A, for example by force fitting therein, and an open lower end 135B, for example cut at an angle, in the lower zone of the flushing bottle 130.

[0111] Under these conditions, the use of the extinguisher 100 is carried out in the following way, the handle 142 being assumed to be initially immobilized by means of the pin 143 in its high position in which the bearing surface 142A does not stress the rod 141, itself in the high position, the cover 134 being intact and sealingly closing the flushing bottle 130; all communication is initially assumed to be closed between the flexible lance tube 190 and the diffusion system or diffuser 1, by the closure means 191. After removing the pin 143, the operator holding the extinguisher 100 in the vertical position illustrated in the figures or in a position close to the vertical, in which the cover 180 is turned upwards, presses the handle 142 to tilt it downwards, which brings the bearing surface 142A into contact with the upper end 141A of the rod 141 then causes the latter to slide downwards inside the bore 184F, with successively bringing the needle 141C into contact with the cover 134 then perforating the latter, which releases the pressurized propellant gas 300 initially contained in the flushing bottle 130.

[0112] The contents of the flush bottle 130 are then released through the radial orifices 153A to be released into the expansion chamber 120' of the tank 120.

[0113] The expansion chamber 120' is then pressurized by the propellant gas 300 coming from the flushing bottle 130 so that the pressure contained in this expansion chamber 120' in turn pressurizes the contents of the tank 120, thus promoting the rise of the fire extinguishing composition 200 through the riser tube 160.

[0114] The operator can then, by acting on the handle 191 A, release at will the fire extinguishing composition 200 which is dispersed thanks to the diffuser 1.

[0115] When the extinguisher 100 is empty or practically empty of the fire extinguishing composition 200, it can be recharged by removing the cover 180, filling it with said fire extinguishing composition through the orifice 123A, replacing the assembly formed by the flushing bottle 130, then empty, and the perforated seal 134, by means of a new flushing bottle 130 containing the desired quantity of pressurized propellant gas 300, closed by a new seal 134 retained at the orifice 133B of the flushing bottle 130, and reassembling the cover 180 thus reequipped.

[0116] EXPERIMENTAL PART:

[0117] Tests were carried out with a fire extinguishing composition according to the invention and a comparative fire extinguishing composition using the technical reference NTA 8133 (November 2021) which describes the performance requirements, test methods and marking of the suitability for extinguishing lithium-ion battery fires.

[0118] The fire extinguishing composition according to the invention comprised a flame retardant, anionic and amphoteric surfactants, foam and thermal stabilizers, and an organic solvent selected from diols, glycols, and glycol ethers in amounts as described above.

[0119] The comparative fire extinguishing composition was a commercial fire extinguishing composition recommended for use in extinguishing lithium-ion battery fires.

[0120] The fire extinguisher used for these tests was the extinguisher according to the invention shown in Figures 1 to 6 and which has been described above. The flushing bottle contained 60 g of carbon dioxide (propellant gas).

[0121] The lithium-ion battery for these tests had a power of 600 Wh. This corresponds to a lithium-ion mountain bike battery. It was composed of 6 sets of 4 flat battery type cells.

[0122] The cell in the center of the lithium-ion battery was charged beyond 100% so that after 7 to 9 minutes it burst and flames appeared. This cell transmitted heat to the other adjacent cells which in turn burst.

[0123] The test was conclusive when at least one cell was intact. To do this, it was checked that its voltage was at least 3.7V. In addition, it was necessary that 2 tests out of a series of 3 tests be successful to validate the test protocol according to the NT A 8133 standard.

[0124] The test was conclusive with the fire extinguishing composition according to the invention but not with the comparative fire extinguishing composition.

Claims

Claims

1. Lithium-ion battery fire extinguishing composition, characterized in that it comprises, in mass percentages expressed relative to the total mass of said composition: - between 0.10% and 0.80%, preferably between 0.30% and 0.70%, of at least one flame retardant, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one amphoteric surfactant, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one anionic surfactant, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one foam stabilizer, - between 0.10% and 1.00%, preferably between 0.15% and 0.70%, of at least one heat stabilizer, - between 0.1% and 2%, preferably between 0.5% and 1%, of at least one organic solvent chosen from diols, glycols and glycol ethers, - Qsp of water,"Qsp" being the acronym for "Quantity sufficient for" to signify that the mass percentage of water in the fire extinguishing composition is such that, added to the percentages of all the other constituents of said fire extinguishing composition, a total of 100% is obtained.,

2. A fire extinguishing composition according to claim 1, characterized in that the flame retardant is selected from the group consisting of ammonium phosphates, phosphate esters, halogenated phosphates, phosphonates, red phosphorus, calcium silicate, sodium silicate, aluminum trihydroxide, magnesium dihydroxide, polybrominated diphenyl ethers, tetrabromobisphenol A, hexabromocyclododecane and bromophenols, taken alone or as a mixture thereof.

3. A fire extinguishing composition according to claim 2, characterized in that the flame retardant is diammonium phosphate and / or ammonium dihydrogen phosphate.

4. Fire extinguishing composition according to any one of claims 1 to 3, characterized in that the amphoteric surfactant is selected from the group consisting of betaines, sultaines, alkylamphoacetates, amphodiacetates, alkylamphopropionates, alkyliminodipropionates, amphodipropionates, aliphatic compounds quaternary ammonium compounds, aliphatic quaternary phosphonium compounds and aliphatic quaternary sulfonium compounds, taken alone or in mixtures thereof.

5. A fire extinguishing composition according to claim 4, characterized in that the amphoteric surfactant is selected from the group consisting of coco dimethyl carboxymethyl betaine, oleyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, lauryl ami-dopropyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine and alkylampho-propionates, taken alone or as a mixture thereof.

6. A fire extinguishing composition according to any one of claims 1 to 5, characterized in that the anionic surfactant is selected from the group consisting of alkylated naphthalene sulfonates, sodium cocoglucoside hydroxypropylsulfonate, sodium cocoglucoside-hydroxypropylsulfonate crosslinked polymers and sodium laurylglucoside-hydroxypropylsulfonate crosslinked polymers, taken alone or as a mixture thereof.

7. A fire extinguishing composition according to any one of claims 1 to 6, characterized in that the organic solvent is selected from the group consisting of ethylene glycol, propylene glycol and dipropylene glycol n-propyl ether, taken alone or as a mixture thereof.

8. Fire extinguishing composition according to claim 1, characterized in that it comprises, in mass percentages expressed relative to the total mass of said composition: - between 0.10% and 0.80%, preferably between 0.30% and 0.70%, of at least one flame retardant chosen from ammonium phosphates, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one amphoteric surfactant chosen from betaines and / or alkylampho-propionates, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one anionic surfactant chosen from alkyl sulfates, alkyl ether sulfates, alkyl ether sulfonates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, ammonium alcohol sulfates, alpha-olefin sulfonates, beta alkoxy alkane sulfonates, alkylauryl sulfonates, alkyl monoglyceride sulfates, alkyl monoglyceride sulfonates, alkyl carbonates,alkyl ether carboxylates, acids,

9. fatty acids, fatty alcohol sulfates, sulfosuccinates, sarcosinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, polyoxyethylene fatty acid amides, isethionates and anionic derivatives of alkyl polyglucosides, taken alone or in mixtures thereof, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one foam stabilizer chosen from aliphatic alcohols and fatty amides containing 8 to 25 carbon atoms, polyethylene glycol and polypropylene glycol, taken alone or as a mixture thereof, - between 0.10% and 1.00%, preferably between 0.15% and 0.70%, of at least one heat stabilizer chosen from ammonium phosphate, ester phosphates, sodium citrate, sucrose, maltose, dextrose, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium sulfate and sodium orthophosphate, taken alone or as a mixture thereof, - between 0.1% and 2%, preferably between 0.5% and 1%, of at least one organic solvent chosen from ethylene glycol, propylene glycol, butyl-di-glycol, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol, n-propyl ether, tri-propylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, dipropylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether, ether ethylene glycol hexyl ether, diethylene glycol hexyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol,monobutyl ether, ethylene glycol monobenzyl ether, diethylene glycol phenyl ether, ethylene glycol phenyl ether, poly(oxy-1,2-ethanediyl), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-butyl ether, ethylene glycol n-butyl ether and dipropylene glycol methyl ether, taken alone or as a mixture thereof, - Qsp of water., A fire extinguishing composition according to claim 1, ca-

10.

11. characterized in that it comprises, in mass percentages expressed in relation to the total mass of said composition: - between 0.10% and 0.80%, preferably between 0.30% and 0.70%, of at least one flame retardant agent chosen from diammonium phosphate and / or ammonium dihydrogen phosphate, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one amphoteric surfactant chosen from the group consisting of coco dimethyl carboxymethyl betaine, oleyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, lauryl amidopropyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, stearyl bis- (2-hydroxypropyl) carboxymethyl betaine and alkylamphopropionates, taken alone or in mixtures thereof, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one anionic surfactant chosen from the group consisting of alkylated naphthalene sulfonates, sodium coco-glucoside hydroxypropylsulfonate, crosslinked polymers of sodium cocoglucoside-hydroxypropylsulfonate and crosslinked polymers of sodium lauryl-glucoside-hydroxypropylsulfonate, taken alone or as a mixture thereof, - between 0.10% and 0.23%, preferably between 0.15% and 0.21%, of at least one foam stabilizer chosen from lauryl, myristic, cetyl alcohol, polyethylene glycol and polypropylene glycol, taken alone or as a mixture thereof, - between 0.10% and 1.00%, preferably between 0.15% and 0.70%, of at least one heat stabilizer chosen from sucrose, maltose and dextrose, taken alone or as a mixture thereof, - between 0.1% and 2%, preferably between 0.5% and 1%, of at least one organic solvent chosen from ethylene glycol, propylene glycol and dipropylene glycol n-propyl ether, taken alone or as a mixture thereof. - Qsp of water. Fire extinguisher (100), characterized in that it comprises a fire extinguishing composition according to any one of claims 1 to 9. A fire extinguisher (100) according to claim 10 comprising: - a sealed tank (120) extending along an axis (Al) and containing the fire extinguishing composition according to any one of claims 1 to 9, said tank (120) is configured to comprise a expansion chamber (120') formed by a part of the reservoir (120) not filled with said fire extinguishing composition, - a flushing bottle (130), sealed and containing a propellant gas (300) under pressure, for use as a propellant for the fire extinguishing composition, the flushing bottle (130) being housed inside the reservoir (120) and having, for the propellant gas (300), an outlet (133B) fluidically connected to the inside of the reservoir (120), characterized in that said fire extinguisher (100) further comprises: - a mixing tube (150) having a 1st end (150A) and a 2nd end (150B), the 1st end (150A) being fluidically connected to the outlet of the flushing bottle (130) and the 2nd end (150B) being closed,said mixing tube (150) comprises at least one lateral orifice (153A) relative to the axis (Al) and which is configured to release the propellant gas (300) into the expansion chamber (120') of said tank (120).,

12. Fire extinguisher (100) according to claim 11, characterized in that the at least one lateral orifice (153A) has a diameter between 0.5 mm and 2.5 mm.

13. Fire extinguisher (100) according to claim 11 or 12, characterized in that the mixing tube (150) has two radial orifices (153A) relative to the axis of the tank (Al).

14. Fire extinguisher (100) according to any one of claims 11 to 13, characterized in that the mixing tube (150) has an internal diameter of between 3 mm and 10 mm and a total length of between 50 mm and 540 mm.

15. Fire extinguisher (100) according to any one of claims 11 to 14, characterized in that it further comprises a riser tube (160) and a flexible lance tube (190), said riser tube (160) is fluidically connected to said flexible lance tube (190) which is provided with sealing closure means (191) and the opening of which is controlled and adjusted to release the fire extinguishing composition according to any one of claims 1 to 9.

16. Fire extinguisher (100) according to any one of claims 11 to 15, characterized in that it comprises a diffusion system (1), configured for spraying the fire extinguishing composition according to any one of claims 1 to 9, which is a Venturi effect diffuser.

17. A method of extinguishing a fire in a lithium-ion battery, characterized in that a fire extinguishing composition according to any one of claims 1 to 9 is sprayed with a fire extinguisher according to any one of claims 10 to 16 onto a burning lithium-ion battery.

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