WO2024038121A1 - Fluides de transfert de chaleur - Google Patents

Fluides de transfert de chaleur Download PDF

Info

Publication number
WO2024038121A1
WO2024038121A1 PCT/EP2023/072630 EP2023072630W WO2024038121A1 WO 2024038121 A1 WO2024038121 A1 WO 2024038121A1 EP 2023072630 W EP2023072630 W EP 2023072630W WO 2024038121 A1 WO2024038121 A1 WO 2024038121A1
Authority
WO
WIPO (PCT)
Prior art keywords
monoalcohol
heat transfer
transfer fluid
monocarboxylic acid
ester
Prior art date
Application number
PCT/EP2023/072630
Other languages
English (en)
Inventor
Francine TOWNSEND
Christopher Inman
Tom Galvin
Mark LASHBROOK
Original Assignee
M & I Materials Development Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB2212107.3A external-priority patent/GB2621628A/en
Application filed by M & I Materials Development Limited filed Critical M & I Materials Development Limited
Publication of WO2024038121A1 publication Critical patent/WO2024038121A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/615—Heating or keeping warm
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6567—Liquids

Definitions

  • Heat transfer fluids This invention relates to heat transfer fluids for use in transferring heat from one location to another, to electrical apparatus comprising such heat fluids, and to methods of using such heat transfer fluids in electrical apparatus.
  • the invention is particularly, although not exclusively, applicable to heat transfer fluids for use in environments where exposure to electricity may occur, and where low temperatures may exist.
  • the invention is illustrated in the following by reference to batteries, but the applicability of the invention is wider.
  • heat transfer fluids are used in transformers. “Lithium plating” is a problem that can arise during the charging of lithium ion batteries. Lithium plating is the deposition of lithium on the anode surface, rather than the desired intercalation of lithium into the anode material.
  • Lithium plating is exacerbated by operating batteries at low temperatures, as this results in reduced ion diffusion and electrolyte conductivity, increasing resistance, and slower kinetics of intercalation of lithium into the anode material. Lithium plating can lead to reduced battery capacity and, in the extreme, short circuiting. Due to the increased internal resistance of cells at sub-zero temperatures and a slowing of the electro-chemical reactions it is therefore necessary to limit input current during battery charging. This in turn can lead to very long charging times for battery systems where the cell temperature is below 0°C.
  • Water/glycol mixtures need to be kept separate from operating electrical components, adding a thermal barrier between components and heat transfer fluid.
  • Such water glycol mixtures may achieve a kinematic viscosity in the region of 100mm2/s at -40°C (see https://detector- cooling.web.cern.ch/data/Table%208-3-1.htm).
  • Hydrocarbons and fluorinated hydrocarbons do not have a good reputation for biodegradability.
  • Esters are known to be biodegradable to varying degrees and to provide good dielectric properties. The esters that have been suggested to date for heat transfer fluids include diesters, but their viscosity at e.g.
  • WO2010/116234 discloses a liquid heat exchange medium comprising 90 or more volume percent of 2-ethylhexyl caprylate (2-ethylhexyl octanoate) and permits presence of other esters of C6-C8 fatty acids with 2 ethyl hexanol.
  • the heat transfer fluids used in the present invention provide heat transfer properties comparable to fluorinated hydrocarbons, viscosity much lower than diesters and commonly used hydrocarbons, and are biodegradable. Further the source materials for the esters described herein are preferably obtainable from biological sources providing environmental benefits to their manufacture and use.
  • the present invention provides electrical apparatus comprising at least one electrical component in thermal contact with a heat transfer fluid, wherein the heat transfer fluid comprises by weight percent of the fluid >95% at least one ester of a C5-C9 monocarboxylic acid and a C5-C9 monoalcohol, the at least one ester having a carbon number of less than 17 the heat transfer fluid not comprising more than 80% by weight 2-ethylhexyl octanoate.
  • the at least one ester may comprise less than 60% by weight 2-ethylhexyl octanoate, less than 40% by weight 2-ethylhexyl octanoate, less than 20% by weight 2-ethylhexyl octanoate, less than 10% by weight 2-ethylhexyl octanoate, or less than 1% by weight 2- ethylhexyl octanoate.
  • the at least one ester may be essentially free of 2-ethylhexyl octanoate.
  • the C5-C9 monocarboxylic acid is optionally an acyclic monocarboxylic acid, for example a linear monocarboxylic acid or a branched monocarboxylic acid.
  • C5-C9 monocarboxylic acid may, as non-limitative examples, include any of pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, 2-ethylhexanoic acid, or 3,5,5-trimethylhexanoic acid.
  • the C5-C9 monoalcohol is optionally an acyclic monoalcohol, for example a linear monoalcohol or a branched monoalcohol and may be a primary, secondary, or tertiary alcohol.
  • the C5-C9 monoalcohol when branched may comprise only methyl branches.
  • C5-C9 monoalcohol may, as non-limitative examples, include any of 2-pentanol, 3-pentanol, 2- hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-octanol, 3-octanol, 4-octanol, 2- nonanol, 3-nonanol, 4-nonanol, 5-nonanol, isononanol, 7-methyloctan-1-ol, 2-ethylhexanol, or 3,5,5-Trimethyl-1-hexanol.
  • the electrical apparatus may comprise a heat source in thermal contact with the heat transfer fluid to permit heat to be transferred by the heat transfer fluid from the heat source to the at least one electrical component.
  • the electrical apparatus may comprise a heat sink in thermal contact with the heat transfer fluid to permit heat to be transferred by the heat transfer fluid from the at least one electrical component to the heat sink.
  • the at least one electrical component may be immersed in the heat transfer fluid.
  • the apparatus may be configured to supply heat to the at least one electrical component when the at least one electrical component is below a first temperature, and to remove heat from the at least one electrical component when the at least one electrical component is above a second temperature.
  • the at least one electrical component may comprise a battery, which may be a lithium ion battery, a lithium metal battery, or any other battery.
  • the heat transfer fluid in the apparatus may comprise by weight percent of the fluid >95% one ester of a C5-C9 monocarboxylic acid and a C5-C9 monoalcohol, and that one ester may be the only ester present.
  • Some of or each at least one ester in the heat transfer fluid optionally has a carbon number of 16 or less or 15 or less.
  • Some of or each at least one ester in the heat transfer fluid optionally has a carbon number of 11 or more, or 12 or more, or 13 or more or 14 or more.
  • the heat transfer fluid in the apparatus may comprise one or more components selected from the group anti-oxidants, metal deactivators, friction modifiers, corrosion inhibitors, antifoam additives, detergents, extreme pressure additives, anti-wear additives, and thermally conductive particles.
  • a method of operating the electrical apparatus comprises transferring heat from the heat transfer fluid to the at least one electrical component, and operating the electrical component once a threshold temperature is exceeded.
  • Specific heat transfer fluids comprising by weight percent:- >95% at least one ester of a C5-C9 monocarboxylic acid and a C5-C9 monoalcohol, the at least one ester having a carbon number of less than 17 and at least one functional additive selected from the group anti-oxidants, metal deactivators, friction modifiers, corrosion inhibitors, antifoam additives, detergents, extreme pressure additives, and anti-wear additives.
  • the functional additives may comprise by weight percent of the fluid:- ⁇ 0.1% anti-oxidant ⁇ 0.001% metal deactivator and optionally the functional additives may comprise by weight percent of the fluid:- 0 .1-1.0% anti-oxidant 0.001-0.05% metal deactivator
  • Fig. 1 shows schematically apparatus showing aspects of the invention as claimed.
  • apparatus 1 houses several electrical components 2 (batteries for example) that are immersed in and so in thermal contact with heat transfer fluid 3 that fills the apparatus.
  • the apparatus comprises heat source 4 and heat sink 5.
  • Heat source 4 can provide heat to the heat transfer fluid 3, and thereby to the electrical components 2.
  • the heat source can be any convenient source, for example an electrical heater, or a heat exchanger with a heating circuit carrying the same or different heat transfer fluid.
  • Heat sink 5 may absorb heat from the heat transfer fluid 3 to remove the heat from the apparatus. Heat may be removed in any convenient way, for example by radiation to ambient, heat exchange with a cooling circuit carrying the same or different heat transfer fluid.
  • the apparatus 1 is shown as a closed unit, with movement of the heat transfer fluid being by convection, but normally a pumped system will be required.
  • the heat transfer fluid is thus capable of transferring heat both to and from a part of the electrical apparatus.
  • the apparatus may be configured to transfer heat to the electrical components when the temperature of said part is below a threshold temperature.
  • a temperature sensor may be used to detect temperature in the apparatus and heat supplied as required to elevate the electrical components to the threshold temperature.
  • having a dielectric liquid with a very low viscosity at -40°C allows more effective transfer of heat from the pre-heating equipment to the battery cells, lower energy demand from pumps and the capability to specify smaller, lighter pumping equipment. This will speed pre- heating of the battery system and allow fast charging current to be applied sooner, as well as making the battery charging more efficient overall. This in turn has the potential to significantly reduce fast charging times under low ambient temperature conditions which brings significant advantages to consumers.
  • Potential applications include, but are not limited to:- ⁇ batteries in vehicles (including without limitation land, air, and marine vehicles); ⁇ stationary battery storage, e.g. batteries for storing renewable energy.
  • Storage units are u sually charged with surplus energy at night when it is colder and therefore the batteries may require preheating; ⁇ non-battery applications requiring a low viscosity, dielectric heat transfer fluid.
  • Performance as a heat transfer fluid depends upon a number of factors, and the Mouromtseff number (Mo) can give an indication of the heat transfer capabilities of fluids.
  • ⁇ is the density
  • k is the thermal conductivity
  • Cp is the specific heat
  • ⁇ is the dynamic viscosity of the heat transfer fluid.
  • the exponents a, b, d and e are system dependent and will differ according to whether there is turbulent flow or laminar flow; but for a defined system provide a means of comparison between heat transfer fluids.
  • the denominator is a function of dynamic viscosity which (over a short range of temperatures and absent any phase changes) can be expected to vary more with temperature than the other factors.
  • Table 1 shows properties for a range of fluids including:- ⁇ the monoesters of the present invention (shown in Part 1 of the Table); ⁇ monoesters not in accordance with the present invention; ⁇ diesters, not in accordance with the present invention; and ⁇ known non-ester heat transfer fluids.
  • the properties shown [indicating units and methods used] are: ⁇ Carbon number (for esters) ⁇ Density at 20°C [kg/dm 3 - ISO 3675] ⁇ Specific Heat at 20°C [J/kg K - ASTM D2766] ⁇ Thermal Conductivity at 40°C [W/m.K - ASTM D7896] ⁇ Kinematic Viscosity at 40°C [mm 2 /s - ISO 3104] ⁇ Kinematic Viscosity at -30°C [mm 2 /s - ISO 3104] ⁇ Kinematic Viscosity at -40°C [mm 2 /s - ISO 3104] ⁇ Pour Point [°C - ISO 3016] ⁇ Flash Point [°C - ISO 2719] Where values are shown with an asterisk * values are estimated or from commercial product data.
  • the C5-C9/C5-C9 monoesters with carbon number less than 17 of the present invention show much lower viscosities at -40°C than the diesters, poly-alphaolefins, or C17 and above monoesters.
  • the esters claimed are dielectric materials permitting direct contact with electrical components. Further having lower or comparable viscosity to a water/glycol mixture enables use of pumps with similar pumping power rather than requiring higher rated pumps.
  • esters claimed Although having viscosities higher than the exemplified fluorinated material, the esters claimed have higher thermal conductivity and specific heat (beneficial for heat transfer as can be seen from the Mouromtseff number equation given above); are environmentally safer, being biodegradable; and further the alcohols and acids from which the esters are made are obtainable from renewable sources. Below carbon number 14 the flash point drops and so carbon numbers of 14 or more may be preferable in some applications.
  • the ester has the formula R1COOR2 wherein R1 and R2 are each hydrocarbon moieties which may be the same or different.
  • Aliphatic moieties are preferred over aromatic moieties and acyclic moieties are preferred over cyclic moieties. Unsubstituted aliphatic moieties are preferred over substituted aliphatic moieties. Aliphatic moieties may be saturated or unsaturated.
  • Additives may include any of antioxidants, metal deactivators, friction modifiers, corrosion inhibitors, antifoam additives, thermally conductive particles or combinations thereof.. Antioxidants limit degradation of the ester.
  • Antioxidants may include, but are not limited to: ⁇ Phenol antioxidants, for example, 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert- b utylphenol; 4,4’-Methylenebis (2,6-di-tertbutylphenol); pentaerythritol tetrakis(3-(3,5- di-tert-butyl-4-hydroxyphenyl)propionate) and butylated hydroxyanisole ⁇ Aromatic amines, for example phenyl alpha naphthylamines and alkylated d iphenylamines Metal deactivators limit degradation of the ester or attack on components.
  • Phenol antioxidants for example, 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert- b utylphenol; 4,4’-Methylenebis (2,6-di-tertbutylphenol); pentaeryth
  • Metal deactivators may include but are not limited to triazole-based deactivators, for example Irgamet® 30, Irgamet® 39, Irgamet® BTZ and Irgamet® TTZ (commercially available from BASF).
  • Friction modifiers limit surface effects with surfaces in contact with the heat transfer fluid. Friction modifiers may include but are not limited to: high hydroxyl esters, , boron derivatives, cyclic and acyclic amides. Corrosion inhibitors limit corrosion of surfaces in contact with the heat transfer fluid.
  • Corrosion inhibitors may include but are not limited to: dimercaptothiazoles, mercaptobenzothiazole, triazoles, imidazoles, alkyl amines, amine phosphates, and sulphonates
  • Antifoam additives limit foaming of the heat transfer fluid.
  • Antifoam additives may include but are not limited to: polyacrylates, and alcohols.
  • Detergents may limit separation of components in the heat transfer fluid or assist in the suspension of any particulate matter. Detergents may include but are not limited to: phosphate esters, sulphonates, phenates and salicylates In some applications extreme pressure additives may be required.
  • Extreme pressure additives may include but are not limited to: graphite, carbon-based nanomaterials, molybdenum disulphide, olefin sulphides, and dithiocarbamates.
  • anti-wear additives may be required to prevent mechanical damage to surfaces that the heat transfer fluid is in contact with.
  • Anti-wear additives include but are not limited to: metal alkylthiophosphates, ashless dithiophosphates, ashless phosphorothioates, ashless thiophosphates, amine phosphates, triarylphosphates, high hydroxyl esters, , sulphurised esters, cyclic and acyclic amides, dimer acids and boron derivatives.
  • thermally conductive particles may include, but are not limited to: graphite, carbon-based nanomaterials, and boron nitride Esters are commonly known compounds and can be manufactured by any suitable process fit for producing esters.
  • alcohol and carboxylic acid (1 equivalent) may be added to a round bottom flask fitted with a Dean-Stark trap and a condenser.
  • the reaction mixture may be heated up to 240 °C under nitrogen, held there for 4 hours and water collected in the Dean-Stark trap. Any excess alcohol or carboxylic acid can then be removed using reduced pressure fractional distillation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Appareil électrique qui comprend au moins un composant électrique en contact thermique avec un fluide de transfert de chaleur, comprenant en pourcentage en poids du fluide plus de 95 % d'au moins un ester d'un acide monocarboxylique en C5-C9 et d'un monoalcool en C5-C9 ayant un nombre de carbones inférieur à 17.
PCT/EP2023/072630 2022-08-19 2023-08-16 Fluides de transfert de chaleur WO2024038121A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB2212107.3A GB2621628A (en) 2022-08-19 2022-08-19 Heat transfer fluids
GB2212107.3 2022-08-19
GB2309679.5A GB2621687A (en) 2022-08-19 2023-06-27 Heat transfer fuids
GB2309679.5 2023-06-27

Publications (1)

Publication Number Publication Date
WO2024038121A1 true WO2024038121A1 (fr) 2024-02-22

Family

ID=87762463

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/072630 WO2024038121A1 (fr) 2022-08-19 2023-08-16 Fluides de transfert de chaleur

Country Status (1)

Country Link
WO (1) WO2024038121A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010116234A1 (fr) 2009-04-09 2010-10-14 Toyota Jidosha Kabushiki Kaisha Milieu échangeur de chaleur et dispositif électrique de stockage
US20120283162A1 (en) 2009-12-28 2012-11-08 Idemitsu Kosan Co., Ltd Base oil for cooling of device, device-cooling oil containing the base oil, device to be cooled by the cooling oil, and device cooling method using the cooling oil
JP5352325B2 (ja) * 2009-04-09 2013-11-27 トヨタ自動車株式会社 蓄電装置および、蓄電装置の放電方法
WO2020132068A1 (fr) * 2018-12-20 2020-06-25 Exxonmobil Research And Engineering Company Fluides caloporteurs à faible viscosité ayant un point d'éclair croissant et une conductivité thermique croissante
US20220131205A1 (en) 2019-03-13 2022-04-28 Total Marketing Services Use of an ester in a cooling composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010116234A1 (fr) 2009-04-09 2010-10-14 Toyota Jidosha Kabushiki Kaisha Milieu échangeur de chaleur et dispositif électrique de stockage
JP5352325B2 (ja) * 2009-04-09 2013-11-27 トヨタ自動車株式会社 蓄電装置および、蓄電装置の放電方法
US20120283162A1 (en) 2009-12-28 2012-11-08 Idemitsu Kosan Co., Ltd Base oil for cooling of device, device-cooling oil containing the base oil, device to be cooled by the cooling oil, and device cooling method using the cooling oil
WO2020132068A1 (fr) * 2018-12-20 2020-06-25 Exxonmobil Research And Engineering Company Fluides caloporteurs à faible viscosité ayant un point d'éclair croissant et une conductivité thermique croissante
US20220131205A1 (en) 2019-03-13 2022-04-28 Total Marketing Services Use of an ester in a cooling composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
AUGUSTUS H GILL AND ET AL: "Viscosity of Esters of Saturated Aliphatic Acids Relation to the Synthesis of Fine Lubricating Oils", 1 May 1935 (1935-05-01), XP055199619, Retrieved from the Internet <URL:http://pubs.acs.org/doi/pdf/10.1021/ie50296a018> [retrieved on 20150702] *

Similar Documents

Publication Publication Date Title
CN101688144A (zh) 离子液体用于改善润滑剂组合物性能的用途
CN113574134A (zh) 酯在冷却组合物中的用途
CN102757838A (zh) 一种超高温润滑脂组合物及其制备方法
CN114317078A (zh) 一种新能源电动汽车多用功能液及其制备方法与应用
JP7155661B2 (ja) 熱伝導性グリース
JP2009161604A (ja) 自動車用変速機油組成物
WO2024038121A1 (fr) Fluides de transfert de chaleur
GB2621687A (en) Heat transfer fuids
JP2014169460A (ja) 自動車用変速機油組成物
JP5613395B2 (ja) 電動モータ油組成物
CN114106787B (zh) 一种冷却介质组合物及其制备方法
CN114555762B (zh) 三唑类型的化合物作为用于改善旨在用于电动或混合动力车辆推进系统的润滑组合物的抗腐蚀性能的添加剂的用途
US20230097290A1 (en) Thermal management system
CN112430454B (zh) 冷却液组合物和冷却系统
US20210087490A1 (en) Ionic liquid containing divalent cation and monovalent anion and lubricant composition comprising same
JP2008001734A (ja) 潤滑油組成物
JP3925958B2 (ja) 軸受油組成物
KR20100035251A (ko) 열효율 향상 및 연료 절감을 위한 열촉매액 조성물 및 이의 제조방법
CN115161097B (zh) 一种电动汽车三合一电桥油的制备方法
CN111718781A (zh) 一种清洁型长寿命液压油
WO2023088773A1 (fr) Compositions de fluide diélectrique comprenant des monoesters de faible viscosité présentant des performances à basse température améliorée
JP2024507927A (ja) 誘電性熱マネジメント流体およびそれらを使用するための方法
JP2019081842A (ja) 熱伝導性グリース
CN117757544A (zh) 油冷电机减速箱传动系统用润滑油组合物及其应用
JP2024507926A (ja) 誘電性熱マネジメント流体およびそれらを使用するための方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23758298

Country of ref document: EP

Kind code of ref document: A1