Coolant containing at least one antifreeze protein

Abstract

The present invention relates to a coolant comprising a) at least one antifreeze protein, b) at least one oligosaccharide, preferably at least one disaccharide, and c) at least one aqueous saline solution. The invention also relates to the use of at least one coolant comprising a) at least one PAG antifreeze protein for cooling a battery, preferably a lithium-ion battery, and / or a motor, preferably an electric motor, for a motor vehicle.

Description

Title of the invention: Cooling fluid comprising at least one antifreeze protein

[0001] The present invention relates to the use of at least one cooling fluid comprising a) at least one PAG antifreeze protein for cooling a battery, preferably a lithium-ion battery, and / or an engine, preferably an electric motor, and / or a propulsion system, preferably for a motor vehicle.

[0002] The invention also relates to a cooling fluid comprising a) at least one antifreeze protein, b) at least one oligosaccharide, preferably at least one disaccharide, and c) at least one aqueous saline solution.

[0003] The aqueous fluids used for cooling engines, for example electric motors, and / or batteries, for example lithium-ion batteries, intended in particular for motor vehicles, preferably hybrid or electric, generally comprise at least one water-soluble organic compound, in particular at least one liquid alcohol, such as glycol, making it possible to lower their freezing point, and water.

[0004] The water-soluble organic compound thus provides an antifreeze function, that is to say that the cooling fluid can remain liquid during its circulation in contact with the different elements of a battery or in the cooling circuits of an engine, at temperatures below 0°C, for example down to temperatures of the order of -20°C or less, while the water provides the heat transfer.

[0005] Coolants are most often used to regulate engine temperature and / or to protect batteries, particularly lithium-ion batteries, from thermal runaway.

[0006] However, water-soluble organic compounds, such as glycol, currently have a number of disadvantages. Glycol can, on the one hand, lead to corrosion of aluminum and / or one of its alloys, present in one or more parts of an engine, and, on the other hand, prove to be harmful to the health and safety of an operator in a factory or in after-sales service.

[0007] In particular, glycol is classified as a toxic chemical substance by European Union regulations (in particular by the "REACH" regulation put in place by the European Parliament and the Council of the European Union entitled "Registration, Evaluation, Authorization and restriction of CHemicals" in English). In this regard, glycol can be irritating to the skin, mucous membranes and eyes, and causes, after ingestion, neurological, cardiovascular and / or acute renal failure.

[0008] For these reasons, safety measures must be taken when storing cooling fluids, and during the assembly, maintenance and recycling of a motor vehicle, a battery or a propulsion system in which the battery is implemented, in order to ensure the protection of operators in the factory and / or in after-sales service.

[0009] Furthermore, the presence of glycol can alter the thermophysical properties of the water within the cooling fluid.

[0010] In other words, cooling fluids comprising a mixture of glycol and water prove to be toxic to the health of operators, pose safety problems and can affect the life of batteries and / or motors.

[0011] In view of the above, one of the objectives of the present invention is therefore to propose a fluid capable of effectively cooling a battery and / or an engine, in particular for motor vehicles, preferably electric or hybrid vehicles, which does not have all of the drawbacks mentioned above, i.e. a non-toxic cooling fluid which does not cause corrosion of one or more parts of a battery and / or an engine while having a freezing temperature lying in a temperature range similar to that of glycol- and water-based cooling fluids.

[0012] In other words, one of the aims of the present invention is to propose a fluid for cooling engines and / or batteries, in particular for motor vehicles, which is non-toxic, has a limited corrosive effect on the parts of an engine and / or a battery, and has improved properties in terms of safety, in particular its storage and / or during the assembly, maintenance and / or recycling of a motor vehicle, a battery and / or a propulsion system.

[0013] The present invention therefore relates in particular to the use of at least one cooling fluid comprising at least one PAG antifreeze protein for cooling a battery and / or an engine and / or a propulsion system, preferably for a motor vehicle.

[0014] The cooling fluid according to the invention thus makes it possible to overcome the previously mentioned drawbacks, that is to say that the fluid is effective for cooling batteries and / or motors, without being toxic to the health of operators, and without being corrosive to the different parts of a motor and / or a battery.

[0015] The PAG antifreeze protein(s) thus makes it possible to effectively lower the freezing point of the coolant.

[0016] The fluid according to the invention has in particular a freezing temperature which can go down to -30°C or less, preferably down to -40°C or less, allowing it to be used effectively at such temperatures for cooling batteries and / or motors.

[0017] In other words, the fluid according to the invention has antifreeze properties similar to those of cooling fluids comprising at least one mixture of glycol and water.

[0018] Thus, thanks to its antifreeze function, the fluid according to the invention can advantageously circulate in liquid form in a device for cooling an engine and / or a battery and / or a propulsion system at temperatures ranging from -40°C to 0°C, in particular from -30°C to 0°C.

[0019] The antifreeze properties of the fluid according to the invention can be measured by cryometry or differential scanning calorimetry, and can be observed by optical microscopy. Preferably, the antifreeze properties are measured by cryometry.

[0020] The fluid according to the invention also makes it possible to ensure better safety for its users, in particular during its storage and / or during the assembly, maintenance and / or recycling of a motor vehicle, a battery and / or a propulsion system.

[0021] In other words, the fluid according to the invention is less dangerous for its users than cooling fluids comprising at least one mixture of glycol and water, including during storage of the fluid and / or during assembly, maintenance and / or recycling of a motor vehicle, a battery and / or a propulsion system.

[0022] The fluid according to the invention advantageously has thermal stability of up to 100°C.

[0023] By "thermal stability" is meant, within the meaning of the present invention, that the fluid does not degrade into volatile compounds capable of forming explosive mixtures with the ambient air. In particular, the degradation can be monitored by fluorescence using a fluorescent marker and the volatile compounds resulting from the degradation can be recovered and analyzed by mass spectroscopy.

[0024] In other words, the fluid according to the invention does not degrade at temperatures of up to 100°C and is slightly flammable.

[0025] The fluid according to the invention has in particular the advantage of not being corrosive with respect to aluminum and / or one of its alloys, which allows it to be used without damaging the different parts of an engine and / or a propulsion system.

[0026] Furthermore, the fluid according to the invention has the advantage of being compatible with several materials which can be used in the manufacture of a battery or a propulsion system comprising at least one motor and at least one battery.

[0027] The fluid according to the invention is in particular compatible with materials based on polymers, such as materials based on polytetrafluoroethylene, poly(p-phenyleneterephthalamide), butadiene-acrylonitrile copolymers, silicone and / or polybutyl.

[0028] Thus the fluid according to the invention makes it possible to protect and extend the life of batteries and / or motors while improving the safety conditions of operators.

[0029] The fluid according to the invention also makes it possible to protect a motor and / or a battery, in particular to provide protection against thermal runaway of a battery, preferably a lithium-ion battery.

[0030] The fluid can advantageously be used in a device for cooling an engine and / or a battery and / or a propulsion system.

[0031] Another object of the present invention is to provide a cooling fluid comprising: a) at least one PAG antifreeze protein, b) at least one oligosaccharide, preferably at least one disaccharide, and (c) at least one aqueous saline solution.

[0032] Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

[0033] In what follows, and unless otherwise indicated, the limits of a domain of values ​​are included in this domain, in particular in the expressions “between” and “ranging from.... to...”.

[0034] Furthermore, the expressions “at least one” and “at least” used in the present description are respectively equivalent to the expressions “one or more” and “greater than or equal”. Use of a coolant

[0035] As indicated previously, the present invention relates to the use of at least one cooling fluid comprising at least one PAG antifreeze protein for cooling a battery and / or an engine and / or a propulsion system, preferably for a motor vehicle. Antifreeze protein PAG

[0036] The cooling fluid according to the invention comprises at least one PAG antifreeze protein, preferably at least two PAG antifreeze proteins.

[0037] The PAG antifreeze protein(s) may be derived from any type of suitable source, for example from among the sources described in the scientific article entitled "Antifreeze proteins and their potential use in frozen food products", Marylin Griffith and K. Vanya Ewart, Biotechnology Advances, vol 13, pp375-402, 1995 and in the patent applications WO 98 / 04699, WO 98 / 04146, WO 98 / 04147, WO 98 / 04148 and WO 98 / 22591.

[0038] The PAG antifreeze protein(s) may be obtained from any type of source by any suitable method, for example by the isolation methods described in the previously mentioned documents.

[0039] The PAG antifreeze protein(s) may be obtained from one or more suitable sources, preferably from two or more suitable distinct sources, including fish, invertebrates, bacteria, plants, fungi and / or algae.

[0040] The antifreeze protein(s) PAG may be derived from fish and, in particular, selected from antifreeze glycoproteins (AFGP) (obtained for example from Atlantic cod, Greenland cod and tomcod), type I PAG (obtained for example from winter flounder, yellowtail flounder, shorttail sculpin and bullhead), type II PAG (obtained for example from sea raven, smelt and Atlantic herring), type III PAG (obtained for example from sea pout, sea bass, red eel, rock spruce and Laval dogfish). An example of the latter is notably described in patent application WO 97 / 02343.

[0041] The PAG antifreeze protein(s) may be derived from invertebrates, preferably arthropods, in particular insects, and / or molluscs, in particular invertebrates chosen from the mealworm (Tenerbrio molitof), the Canadian fire beetle (Dendroïdes canadensisp), the spruce budworm (choristoneura fumiferana) and the wood frog (Rana sylvatica).

[0042] The PAG antifreeze protein(s) may be derived from bacteria, in particular Marinomona sprimoryensis.

[0043] The PAG antifreeze protein(s) may be derived from plants, and in particular from plants selected from garlic herb (Alliarapetiolatd), blue aster, spring oats, winter cress, winter rapeseed, Brussels sprouts, carrot, hooded dandelion (Dicentra cucullariap), spurge, daylily, winter barley, Virginia waterweed (Hydrophyllum virginianum), plantago, narrow-leaved plantain, convoluted heteropogon, Kentucky bluegrass, white oak, winter rye, bittersweet nightshade, potato, chickweed (white pimpernel), dandelion, spring and winter wheat, triticale, periwinkle (Vinca), violet and grasses, Perennial Ryegrass (Lolium pe reinne) and Antarctic hairgrass (Deschampsia antartica E. desv).

[0044] The PAG antifreeze protein(s) may be derived from fungi, in particular leucosporidium.

[0045] The PAG antifreeze protein(s) may be derived from algae, in particular among the Chaetocerotaceae, in the Chaetocerotaceae neogracile.

[0046] In accordance with the present invention, both natural species and species obtained by genetic modification can be used. For example, microorganisms or plants can be genetically modified to express the PAG antifreeze protein(s) according to the invention.

[0047] Thus, genetic manipulation methods can be used to produce the PAG antifreeze protein(s) according to the invention.

[0048] Genetic manipulation methods used to produce PAGs having at least 80%, preferably more than 95%, preferably 100% homology with PAGs directly obtained from natural sources. For the purposes of the present invention, such PAG antifreeze proteins having this high level of homology are also encompassed within the term "PAG".

[0049] Genetic manipulation techniques may be used as follows: A suitable host cell or organism is transformed with a genetic construct containing the desired polypeptide. The nucleotide sequence encoding the polypeptide may be inserted into a suitable expression vector encoding the elements necessary for transcription and translation and such that they are expressed under appropriate conditions (e.g., in the correct orientation and reading frame and with appropriate targeting and expression sequences). The methods necessary for the construction of such expression vectors are well known to a person skilled in the art.

[0050] A number of expression systems may be used to express the coding sequence of the polypeptide. These include, but are not limited to, bacteria, yeast insect cell systems, plant cell culture systems, and plants, all transformed using appropriate expression vectors.

[0051] A wide variety of plants and plant cell systems can be transformed with the nucleic acid constructs of the desired polypeptides. Preferred embodiments include, but are not limited to, corn, tomato, tobacco, carrot, strawberry, rapeseed, and sugar beet.

[0052] Preferably, the fluid according to the invention comprises at least two distinct antifreeze proteins, which may come from one or more distinct sources, such as those described previously.

[0053] Preferably, the fluid according to the invention comprises one or more PAG antifreeze proteins obtained from one or more sources, preferably from two or more sources, chosen from fish, invertebrates, bacteria, plants, fungi and / or algae, preferably chosen from plants.

[0054] Preferably, the fluid according to the invention comprises at least one antifreeze protein PAG, preferably at least two antifreeze proteins, chosen from type I PAG, type II PAG, type II PAG, type IV PAG, AFGP natural glycoproteins, PAG from the mealworm (Tenerbrio molitof), PAG from the Canadian fire beetle (Dendroïdes canadensis), PAG from the spruce budworm (Choristoneura fumiferana), PAG from Marinomona sprimoryensis, PAG from Leucosporidium, PAG from perennial ryegrass, PAG from Chaetocerotaceae neogracile, wood frog (Rana sylvatica) and Antarctic hairy locust (Deschampsia antartica E. desv) and mixtures thereof.

[0055] Preferably, the cooling fluid according to the invention comprises at least one PAG antifreeze protein derived from plants, more preferably chosen from perennial ryegrass (Perennial Ryegrass Lolium perenne) and Antarctic hairgrass (Deschampsia antartica E. desv).

[0056] Preferably, the PAG antifreeze protein(s) is or are present in the cooling fluid according to the invention in a concentration ranging from 10 μg / mL to 2 mg / ml, more preferably from 15 μg / mL to 1.5 mg / ml, in the fluid according to the invention. Oligosaccharide(s)

[0057] Preferably, the cooling fluid according to the invention further comprises b) at least one oligosaccharide.

[0058] For the purposes of the present invention, the term "oligosaccharide" means oligoholosides or oligosides, which are oligomers formed from a number of n oses (or monosaccharides) linked by one or more alpha or beta glycoside bonds; the number n corresponds to an integer varying from 2 to 10, preferably varying from 2 to 6, better still from 2 to 4.

[0059] The oligosaccharide(s) may be chosen from the group consisting of fructo-oligosaccharides, gluco-oligosaccharides, galacto-oligosaccharides, mannan-oligosaccharides, pyrodextrins, isomalto-oligosaccharides, xylooligosaccharides, transgalacto-oligosaccharides and mixtures thereof.

[0060] Preferably, the oligosaccharide(s) is(are) chosen from fructo-oligosaccharides, gluco-oligosaccharides, and mixtures thereof.

[0061] The fructo-oligosaccharide(s) may be prepared by hydrolysis of rinulin or by enzymatic synthesis from sucrose.

[0062] The gluco-oligosaccharide(s) can be synthesized by a transglucosylation reaction catalyzed by enzymes of the glucan-sucrase family.

[0063] Preferably, the oligosaccharide(s) is(are) chosen from disaccharides (also called diholosides).

[0064] Preferably, the disaccharide(s) is(are) chosen from reducing or non-reducing disaccharides, more preferably chosen from disaccharides non-reducing.

[0065] The disaccharide(s) may be reducing and chosen from maltose, lactose and cellobiose.

[0066] The disaccharide(s) may be non-reducing and chosen from trehalose, sucrose and mixtures thereof.

[0067] Preferably, the cooling fluid according to the invention comprises b) at least one oligosaccharide chosen from maltose, lactose, cellobiose, trehalose, sucrose, and mixtures thereof.

[0068] Preferably, the cooling fluid according to the invention comprises b) at least one oligosaccharide, more preferably chosen from disaccharides, better still from trehalose, sucrose and their mixtures.

[0069] Preferably, the content of oligosaccharide(s) varies from 1 to 40% by weight, more preferably in a content ranging from 5 to 30% by weight, better still in a content ranging from 8 to 27% by weight, relative to the total weight of the fluid.

[0070] The cooling fluid comprises in particular water, preferably an aqueous saline solution. Saline aqueous solution

[0071] Preferably, the cooling fluid according to the invention further comprises c) at least one aqueous saline solution.

[0072] The aqueous saline solution is in particular an aqueous saline buffer solution, preferably at neutral pH, that is to say having a pH ranging from 7.0 to 7.9, preferably ranging from 7.0 to 7.5.

[0073] Preferably, the saline buffer solution comprises at least one (bi)carbonate salt, a phosphate salt or a citrate salt.

[0074] Preferably, the saline buffer solution is selected from a potassium phosphate buffer solution, a borate buffer solution, a citrate buffer solution, a sodium phosphate buffer solution, or a carbonate buffer solution.

[0075] Preferably, the aqueous saline solution is present in the cooling fluid in a content ranging from 10 to 90% by weight, relative to the total weight of the fluid.

[0076] According to a preferred embodiment, the cooling fluid according to the invention comprises: a) at least one PAG antifreeze protein as defined previously, b) at least one oligosaccharide as defined previously, and c) at least one aqueous saline solution, as defined previously.

[0077] According to this preferred embodiment, the fluid advantageously comprises: a) at least one PAG antifreeze protein from plants, more preferably chosen from perennial ryegrass (Lolium perenne) and Antarctic hairgrass (Deschampsia antarticap) b) at least one oligosaccharide chosen from disaccharides, preferably chosen from trehalose, sucrose and their mixtures, c) at least one aqueous saline solution, in particular a buffer having a pH ranging from 7.0 to 7.9, preferably comprising at least one phosphate salt. Additive(s)

[0078] The cooling fluid may further comprise one or more additives, preferably chosen from natural corrosion inhibitors, extracted from plants, gum, such as flavonoids, glycosides, alkaloids, saponins, phytosterol, tannins, anthraquinones and phenolic compounds, natural antifoams (also called anti-biofouling) extracted from plants or bacteria or fungi such as the species Morus rubra, Rhodophyta sp, Chromobacterium violacein, Paracoccus carotinifaciens.

[0079] These additives may be present in the fluid according to the invention in an amount ranging from 0 to 2% by weight, relative to the total weight of the fluid according to the invention.

[0080] The cooling fluid is preferably free of glycol, more preferably of any water-soluble liquid alcohol.

[0081] Use for cooling a battery and / or motor and / or a propulsion system

[0082] The fluid according to the invention, as defined above, is used for cooling a battery and / or an engine and / or a propulsion system, preferably for a motor vehicle.

[0083] Preferably, the invention relates to the use of at least one cooling fluid according to the invention comprising: a) at least one PAG antifreeze protein as defined above, b) at least one oligosaccharide as defined above, and c) at least one aqueous saline solution, as defined above, for cooling a battery and / or an engine and / or a propulsion system, preferably for a motor vehicle.

[0084] For the purposes of the present invention, the term "propulsion system" means a system enabling the propulsion of a vehicle, in particular an electric vehicle. The propulsion system includes in particular an electric motor, a transmission and a battery.

[0085] Preferably, the fluid according to the invention circulates in a device for cooling an engine and / or a battery and / or a propulsion system.

[0086] Preferably, the aqueous fluid according to the invention circulates in a fluid exchanger.

[0087] The motor is preferably an electric motor, a combustion engine or a hybrid engine, more preferably an electric or hybrid engine.

[0088] The battery is preferably a lithium-ion battery.

[0089] Preferably, the fluid according to the invention is used for cooling a lithium-ion battery and / or a hybrid or electric motor, in particular for a motor vehicle, in particular a hybrid or electric vehicle.

[0090] Advantageously, the fluid according to the invention also makes it possible to protect an engine and / or a battery against thermal runaway.

[0091] Preferably, the fluid provides protection against thermal runaway of a lithium-ion battery. Coolant

[0092] Another subject of the present invention relates to a cooling fluid comprising a) at least one PAG antifreeze protein as defined previously, b) at least one oligosaccharide as defined previously, and c) at least one aqueous saline solution, as defined previously.

[0093] Preferably, the cooling fluid comprises: a) at least one PAG antifreeze protein derived from plants, more preferably chosen from perennial ryegrass (Perennial Ryegrass Lolium perenne) and Antarctic hairgrass (Deschampsia antarticap b) at least one oligosaccharide chosen from disaccharides, preferably chosen from trehalose, sucrose and their mixtures, c) at least one aqueous saline solution, in particular a buffer having a pH ranging from 7.0 to 7.9, preferably comprising at least one phosphate salt.

[0094] The invention is illustrated in more detail in the following non-limiting examples. Examples

[0095] The following examples serve to illustrate the invention without limiting it. Example 1

[0096] A cooling fluid is prepared comprising: a) an antifreeze protein of the Deschampsia antartica E. desv type (PAG from Antarctic squid) in a content of 1 mg / ml, b) 10% by weight of trehalose relative to the total weight of the fluid, c) a phosphate buffer saline solution at pH = 7.4.

[0097] The cooling fluid obtained has antifreeze properties down to -25°C, measured by cryometry or differential scanning calorimetry, and can be observed by optical microscopy. Example 2

[0098] A cooling fluid is prepared comprising: a) an antifreeze protein of the Perennial Ryegrass Lolium perenne type (PAG from perennial ryegrass) in a content of 20 ql / ml, b) 25% by weight of sucrose relative to the total weight of the fluid, c) a phosphate buffer saline solution having a pH = 7.0.

[0099] The cooling fluid obtained has antifreeze properties down to -25°C, measured by cryometry or differential scanning calorimetry, and can be observed by optical microscopy.

[0100] Furthermore, the fluid obtained has a thermal stability of up to 100°C.

Claims

Claims

1. Use of at least one cooling fluid comprising at least one PAG antifreeze protein for cooling a battery and / or an engine and / or a propulsion system, preferably for a motor vehicle.

2. Use according to claim 1, characterized in that the PAG antifreeze protein(s) is or are obtained from one or more sources, preferably from two or more sources, chosen from fish, invertebrates, bacteria, plants, fungi and / or algae, preferably chosen from plants.

3. Use according to claim 1 or 2, characterized in that the PAG antifreeze protein(s) is or are chosen from type I PAG, type II PAG, type II PAG, type IV PAG, natural AFGP glycoproteins, PAG from the mealworm (Tenerbrio molitor), PAG from the Canadian firefly (Dendroides canadensis). PAG from spruce budworm (Choristoneura fumiferana), PAG from marinomona sprimoryensis, PAG from leucosporidium, PAG from perennial ryegrass, PAG from Chaetocerotaceae neogracile, wood frog (Rana sylvatica) and Antarctic cane ÇDeschampsia antartica E. desv) and their mixtures, preferably chosen from perennial ryegrass (Perennial Ryegrass Lolium perenne) and Antarctic cane (Deschampsia antartica E. desv).

4. Use according to any one of the preceding claims, characterized in that the PAG antifreeze protein(s) is or are present in said fluid at a concentration ranging from 10 qg / mL to 2 mg / ml, more preferably from 15 qg / mL to 1.5 mg / ml.

5. Use according to any one of the preceding claims, characterized in that the fluid further comprises at least one oligosaccharide, preferably chosen from the group consisting of fructo-oligosaccharides, gluco-oligosaccharides, galacto-oligosaccharides, mannan-oligosaccharides, pyrodextrins, isomalto-oligosaccharides, xylo-oligosaccharides, transgalacto-oligosaccharides and mixtures thereof, preferably chosen from fructo-oligosaccharides, gluco-oligosaccharides, and mixtures thereof.

6. Use according to the preceding claim, characterized in that the oligosaccharide(s) is(are) chosen from maltose, lactose, cellobiose, trehalose, sucrose, and mixtures thereof, preferably among trehalose, sucrose and mixtures thereof.

7. Use according to claim 5 or 6, characterized in that the oligosaccharide content varies from 1 to 40% by weight, more preferably in a content ranging from 5 to 30% by weight, better still in a content ranging from 8 to 27% by weight, relative to the total weight of the fluid.

8. Use according to any one of the preceding claims, characterized in that the fluid further comprises at least one aqueous saline solution, preferably an aqueous saline buffer solution having a pH ranging from 7.0 to 7.9, more preferably ranging from 7.0 to 7.

5.

9. Use according to the preceding claim, characterized in that the aqueous saline buffer solution is chosen from a potassium phosphate buffer solution, a borate buffer solution, a citrate buffer solution, a sodium phosphate buffer solution, or a carbonate buffer solution.

10. Use according to any one of the preceding claims, characterized in that the fluid circulates in a cooling device of an engine and / or a battery and / or a propulsion system.

11. Use according to any one of the preceding claims, characterized in that the battery is a lithium-ion battery.

12. Use according to any one of the preceding claims, characterized in that the motor is an electric motor, a combustion engine or a hybrid motor, preferably an electric motor or a hybrid motor.

13. Cooling fluid comprising: a) at least one PAG antifreeze protein, as defined according to any one of claims 1 to 4, b) at least one oligosaccharide as defined according to any one of claims 5 to 7, c) at least one aqueous saline solution as defined as defined according to claim 8 or 9.