Compositions containing fluorine-substituted ethers, as well as methods and uses thereof.

Abstract

A method for heating and / or cooling electronic components, articles, and devices during their operation and / or manufacture, by providing a refrigerant comprising 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane ((CF3)2CHOCF2CHFCF3) and / or 1,1,1,2,3,3,-hexafluoro-3-(2,2,2-trifluoroethoxy)propane ((CF3)CH2OCF2CHFCF3).

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 415,679, filed Oct. 13, 2022, which is incorporated herein by reference.

[0002] (Field of the Invention) This disclosure relates to the use of fluorine - substituted ethers and their use as heat transfer fluids in various applications related to the manufacture of semiconductor devices.

Background Art

[0003] In order to meet the requirements of various applications, inert fluorinated fluids with a low global warming potential while providing high thermal stability, low toxicity, non - flammability, good solvency, and a wide operating temperature range are still needed.

[0004] Applicants have come to understand that the development of new compounds and compositions for use in many important applications is associated with many difficult problems. In particular, applicants have recognized the need for compositions, methods, and systems that are environmentally acceptable (low GWP and low ODP), non - flammable, and have low or no toxicity, and have one or more of the properties required for a particular application. For example, a refrigerant should provide appropriate heat transfer properties over the use temperature for a particular heat transfer application, and should also have an appropriately low dielectric constant if the heat transfer application involves exposure or potential exposure of the refrigerant to electronic devices or components. An example of such use with a continuing need for improved refrigerants is the transfer of heat required to manage / control the temperature of electronic components, devices, and articles during the processes used to manufacture and fabricate them. This is a substantial technical challenge because refrigerants often need to operate effectively over a relatively wide range of processing conditions, including process temperatures, and during potential exposure to electronic devices during such processing.

[0005] Examples of electronic manufacturing processes that experience thermal management challenges include, in particular, etching and rapid thermal annealing (RTA) of semiconductor integrated circuits as their linewidth continues to decrease. These manufacturing challenges involve the increasing need to achieve effective and relatively precise temperature control of certain fluids and / or components used in the manufacturing process. See, for example, U.S. Patent No. 5,904,572 (relating to a wet etching process), U.S. Patent Publication No. 2005 / 0155555 (relating to vapor deposition in semiconductor manufacturing), and U.S. Patent Publication No. 2007 / 0117362 (relating to RTA), each of which is incorporated herein by reference. These challenges are highlighted because, in certain electronic cooling applications, the viscosity of the refrigerant fluid used to control the temperature of electronic components also needs to be low enough to allow the fluid to circulate and maintain its desired heat transfer properties within the operating temperature range of the refrigerant fluid.

[0006] Vapor-phase soldering is another example of an electronics manufacturing process that utilizes a coolant to help control the processing temperature. High temperatures are used in this application, and therefore the heat transfer fluid must be suitable for high-temperature exposure (e.g., up to 250°C). Currently, perfluoropolyethers (PFPEs, i.e., compounds containing only carbon, oxygen, and fluorine) are commonly used as heat transfer fluids in this application. While many PFPEs have adequate thermal stability at these high temperatures, they are environmentally persistent with extremely long atmospheric lifetimes, thereby generating very high global warming potentials (GWPs).

[0007] Another need for improved refrigerants arises in relation to the manufacture and / or operation of miniature electronic devices. The continuous desire to miniaturize electronic components while adding functionality increases the thermal power density of operating devices, and therefore makes cooling the electronic components within such devices more difficult. As a general rule, increasing computing power in desktop computers, data centers, and communication centers leads to increased thermal output when such devices are operating, again making thermal management of electronic devices during manufacture and / or operation increasingly important, difficult, and demanding.

[0008] Another example of the challenges in providing refrigerants for thermal management is the increasing use of electric vehicles, particularly cars, trucks, and motorcycles. In electric vehicles, thermal management is especially critical and challenging for several reasons, including the critical need to cool and / or heat the battery in a reliable, efficient, and safe manner, while remaining within a relatively narrow temperature range. As the demand for battery-powered vehicles with wider ranges and faster charging increases, the challenges of providing effective thermal battery management are becoming even greater.

[0009] The efficiency and effectiveness of batteries, especially those supplying power to electric vehicles, are a function of the operating temperature in which they operate. Therefore, thermal management systems must frequently be able to do more than simply remove heat from batteries during operation and / or charging; that is, they must be able to achieve cooling over a relatively narrow temperature range using equipment that is as low-cost and as lightweight as possible. This creates a need for refrigerants in such systems, which have a difficult combination of physical and performance characteristics to achieve. Furthermore, in some critical applications, thermal management systems must be able to heat the battery, especially when the vehicle is started in cold weather, which makes it even more difficult to discover, develop / obtain effective compounds and / or compositions in such systems, not only from the standpoint of thermal performance but also from a multitude of other viewpoints, including environmental, safety (flammability and toxicity), dielectric properties, etc.

[0010] As a specific example of the importance of dielectric constant, one frequently used system for thermal management of electric vehicle batteries involves immersing the battery in a fluid used for thermal management. Such a system imposes the further constraint that the fluid used within such a system must be electronically compatible with close contact with the battery or other electronic devices or components while the battery or device is operating. Generally, this means not only that the fluid must be non-flammable, but also that the fluid must have low conductivity and a high level of stability while in contact with the battery or other electronic components, while the components are operating and relatively high temperatures exist during operation. The applicants have come to understand that such properties are also desirable in the indirect cooling of operating electronic devices and batteries, since any leakage of such a fluid can result in contact with operating electronic components.

[0011] Water / glycol combinations have been commonly used for battery cooling, including immersion cooling, and other classes of materials, including some chlorofluorocarbons, fluorohydrocarbons, chlorohydrocarbons, and hydrofluoroethers, have been mentioned as possible uses. See, for example, U.S. Patent Application Publication No. 2018 / 0191038.

[0012] U.S. Patent Application Publication No. 2023 / 0200010 discloses the use of certain fluorinated ethers for cooling electronic devices by at least partially immersing the electronic devices in a fluorinated fluid said to have a boiling point of 50°C to 60°C.

[0013] Japanese Patent Application Publication No. 2005 / 047856 discloses the use of several fluorinated ether compounds for use as refrigerants, cleaning agents, and the like.

[0014] A fluorinated ether compound according to the following formula, (F3C)2CH-O-CH n F 2-n -CH m F 3-m In the formula, n is 1 or 2, and when n is 1, m is any integer from 0 to 3, but when n is 2, m is 0 or 2, and the compound has been proposed for use as a solvent for various fluorine-containing polyethers in particular. See Japanese Patent Application Publication No. 202105950. This document shows that embodiments of the above formula, said to have a 3-1 configuration (to be understood as meaning m=3 and n=1), have additional uses including drainage agents, foaming agents, heat transfer media, and fire extinguishing agents, but such uses are not specifically described or illustrated.

[0015] Accordingly, the applicants have come to recognize, among other needs described herein, a particular need for thermal management methods and systems using refrigerants that are environmentally acceptable (relatively low GWP and low ODP), non-flammable, low-toxicity or non-toxic, and have excellent thermal properties that provide effective cooling and / or heating, especially in electronic and semiconductor manufacturing processes involving relatively high temperatures, and / or for use in maintaining process conditions over a relatively narrow temperature range. For example, the applicants have found that fluids with relatively low boiling points (e.g., below about 60°C) are undesirable in many applications, including the manufacture of electronic components, as will be further described below. [Overview of the project]

[0016] The present invention includes a composition comprising 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane (hereinafter sometimes referred to as "HFPOHFP" in this specification). The composition according to this paragraph may be referred to as composition 1A in this specification for convenience.

[0017] The present invention includes compositions comprising 1,1,1,2,3,3,-hexafluoro-3-(2,2,2-trifluoroethoxy)propane, or the aforementioned combinations. The compositions according to this paragraph may be referred to herein as composition 1B for convenience.

[0018] The present invention includes compositions comprising a combination of 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane and 1,1,1,2,3,3,-hexafluoro-3-(2,2,2-trifluoroethoxy)propane. The compositions according to this paragraph may be referred to herein, for convenience, as Composition 1C.

[0019] The present invention includes a refrigerant comprising HFPOHFP. The refrigerant according to this paragraph may be referred to as Refrigerant 1 for convenience in this specification.

[0020] The present invention includes a refrigerant containing at least about 10% by weight of HFPOHFP. The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 2.

[0021] The present invention includes a refrigerant containing at least about 50% by weight of HFPOHFP. The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 3.

[0022] The present invention includes a refrigerant containing at least about 75% by weight of HFPOHFP. The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 4.

[0023] The present invention includes a refrigerant containing at least about 90% by weight of HFPOHFP. The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 5.

[0024] The present invention includes a refrigerant consisting essentially of HFPOHFP. The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 6.

[0025] The present invention includes a refrigerant consisting of HFPOHFP. The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 7.

[0026] The present invention includes a refrigerant containing 1,1,1,2,3,3,-hexafluoro-3-(2,2,2-trifluoroethoxy) propane (hereinafter may be referred to as "TFE / HFP" herein). The refrigerant according to this paragraph may be referred to herein for convenience as Refrigerant 8.

[0027] The present invention includes a method for synthesizing a fluoroether from a fluoroalkene and a fluoroalcohol, which includes reacting the fluoroalcohol with the fluoroalkene in the presence of a catalyst to obtain a fluoroether. The method according to this paragraph may be referred to herein for convenience as Synthesis Method 1.

[0028] The present invention includes a method for cooling and / or heating an operating electronic device and / or electronic component, device, or article during its manufacturing process, the method comprising providing a refrigerant containing HFPOHFP, each of refrigerants 1 to 7, and heating and / or cooling the electronic component, device, or article by thermally connecting it to the refrigerant, preferably by immersing at least a portion of the electronic component, device, or article in the refrigerant. The method according to this paragraph may be referred to herein for convenience as heat transfer method 1A.

[0029] The present invention includes a method for cooling and / or heating an electronic component, device, or article during its manufacturing process, the method comprising providing a refrigerant containing HFPOHFP, each of refrigerants 1 to 7, and thermally connecting the electronic component, device, or article to the refrigerant to heat and / or cool the electronic component, device, or article during the manufacturing process of the electronic component, device, or article. The method according to this paragraph may be referred to herein for convenience as heat transfer method 1B. [Brief explanation of the drawing]

[0030] By considering the attached drawings and referring to the following description of embodiments of the present disclosure, the and other characteristics mentioned herein, as well as the manner in which they are achieved, will become clearer, and the disclosure itself will be better understood. [Figure 1] This is a schematic diagram of the thermal management system of the present invention. [Figure 2A] This is a schematic diagram of a first exemplary immersion cooling system according to the present invention. [Figure 2B] This is a schematic diagram of a second exemplary immersion cooling system according to the present invention. [Figure 3A] This is a schematic diagram illustrating a battery thermal management system according to one embodiment of the present invention. [Figure 3B] This is a schematic diagram illustrating a battery thermal management system according to one embodiment of the present invention. [Figure 4] This is a photograph showing a battery thermal management system according to one embodiment of the present invention. [Figure 5] This is an illustrative circuit diagram of an organic Rankine cycle. [Figure 6] This is an example circuit diagram of a heat pump. [Figure 7] This is a circuit diagram of an example of a secondary loop system. [Figure 8] This is a semi-circular diagram of an example of a lithium-ion battery cooling system using the composition of the present invention. [Figure 9] This is a semi-circular diagram of an example of a lithium-ion battery having the electrolyte composition of the present invention. [Figure 10] This is a semi-circular diagram of a heat pipe using the heat transfer composition of the present invention. [Figure 11] This is a side cross-sectional view of a conventional wet etching station. [Modes for carrying out the invention]

[0031] I. Definition The terms "R-1132(E)", "HFO-1132(E)", and "trans-HFO-1132(E)" each refer to the trans isomer of 1,2-difluoroethylene.

[0032] The terms "R-1132a" and "HFO-1132a" refer to 1,1-difluoroethylene, respectively.

[0033] The terms "R-1234yf" and "HFO-1234yf" refer to 2,3,3,3-tetrafluoropropene.

[0034] The terms "R-1234ze(E)" and "HFO-1234ze(E)" refer to the trans isomers of 1,3,3,3-tetrafluoropropene.

[0035] The terms "R-1233zd(E)" and "HFCO-1233zd(E)" refer to the trans isomer of 1-chloro-3,3,3-trifluoropropene.

[0036] The terms "R-1233zd(Z)" and "HFCO-1233zd(Z)" refer to the cis isomers of 1-chloro-3,3,3-trifluoropropene.

[0037] The terms "R-1224yd(E)" and "HFCO-1224yd(E)" refer to the trans isomer of 1-chloro-2,3,3,3-tetrafluoropropene.

[0038] The terms "R-1224yd(Z)" and "HFCO-1224yd(Z)" refer to the cis isomers of 1-chloro-2,3,3,3-tetrafluoropropene.

[0039] The terms "R-1336mzz(E)" and "HFO-1336mzz(E)" refer to the trans isomer of 1,1,1,4,4,4-hexafluorobutene-2-ene.

[0040] The term "HFE-7000" refers to 1-methoxyheptafluoropropane (C3F7OCH3).

[0041] The term "HFE-7100" refers to 1-methoxy-nonafluorobutane (C4F9OCH3).

[0042] The term "HFE-7200" refers to ethoxynonafluorobutane (C4F9OC2H5).

[0043] The term "HFE-7300" refers to 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethylpentane.

[0044] The term "HFE-7500" refers to 2-trifluoromethyl-3-ethoxide decofluorohexane.

[0045] Where used herein, references to defined groups such as "RB1-RB2" (see Table 4 below) refer to each refrigerant blend within that group, including cases where the definition number includes a suffix. Thus, references to "RB1-RB2" include references to each RB1A, RB1B, etc., and RB2A, RB2B, etc.

[0046] The compound names used herein, along with their corresponding chemical names and formulas, are shown in Table 1 below.

[0047] [Table 1]

[0048] The terms “electronic device” and related terms mean a device or component of a device that is in the process of performing its intended function by receiving and / or transmitting and / or generating electrical energy and / or electronic signals. Therefore, as used herein, the term “operating electronic device” includes, for example, a battery in the process of supplying a source of electrical energy to another component, and, for example, a battery being charged or recharged.

[0049] The term "refrigerant" and related forms mean a fluid (liquid or gas) used to transfer heat or energy to and / or from a fluid, article, or device (for heating).

[0050] The terms "operating electronic device" and related terms mean a device or component of a device that is in the process of performing its intended function by receiving and / or transmitting and / or generating electrical energy and / or electronic signals. Therefore, as used herein, the term "operating electronic device" includes, for example, a battery in the process of supplying a source of electrical energy to another component, and a battery being charged or recharged.

[0051] Thermal contact and related forms include direct contact with a surface and indirect contact through another object or fluid that facilitates the flow of heat between the surface and the fluid.

[0052] Thermal conductivity refers to the dielectric breakdown voltage in kV, measured according to ASTM D7896-19.

[0053] The Global Warming Potential ("GWP") was developed to allow comparisons of the global warming impacts of different gases. It measures how much energy is absorbed over a given period by one ton of a given gas release, relative to one ton of carbon dioxide release. A higher GWP indicates that a given gas will warm the Earth more than CO2 over that period. The period typically used for GWP is 100 years. GWP provides a common measure that allows analysts to sum up emission estimates for different gases.

[0054] "LC50" is a measure of the acute toxicity of a compound. The acute inhalation toxicity of a compound can be evaluated using the test method described in OECD Guideline for Testing of Chemicals No. 403 "Acute Inhalation Toxicity" (2009), Method B.2. (Inhalation) of Commission Regulation (EC) No. 440 / 2008.

[0055] The term AMES negative refers to a compound or composition that returns a negative result when tested under the Ames test as defined in the Toxic Substances Control Act of the United States.

[0056] The flash point is determined according to ASTM D3828-16a and refers to the lowest temperature at which a liquid vapor continues to burn after the ignition source has been removed.

[0057] In the context of heat management compositions or heat transfer compositions containing fluids, "non-flammable" means a compound or composition that does not have a flash point below 100°F (37.8°C) according to NFPA30:Flammable and Combustible Liquid Code. The flash point of a heat management composition or fluid is determined according to ASTM D3828-16a, and refers to the lowest temperature at which the vapor of the composition continues to burn after the ignition source has been removed.

[0058] In the context of refrigerant compositions, compounds or compositions that are non-flammable and of low or no toxicity are classified as "A1" according to ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and Annex B1 of ASHRAE Standard 34-2016.

[0059] Non-toxic or low-toxicity means a fluid classified as Class "A" according to ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and as described in Annex B1 of ASHRAE Standard 34-2016.

[0060] "Capacity" is the amount of cooling in units of BTU / hr provided by a refrigerant in a cooling system. This is experimentally determined by multiplying the change in enthalpy of the refrigerant in BTU / lb as it passes through the evaporator by the mass flow rate of the refrigerant. Enthalpy can be determined from measurements of the pressure and temperature of the refrigerant. The capacity of a cooling system relates to its ability to maintain the area being cooled at a specific temperature. The capacity of a refrigerant represents the amount of cooling or heating it provides, and provides a certain degree of the compressor's ability to pump and deliver the amount of heat for a given volumetric flow rate of the refrigerant. In other words, given a particular compressor, a refrigerant with higher capacity will provide more cooling or heating power.

[0061] The "Coefficient of Performance" (COP) is a widely accepted measure of refrigerant performance, particularly useful for representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving vaporization or condensation of the refrigerant. In refrigeration engineering, the term represents the ratio of useful refrigeration or cooling capacity to the energy applied by the compressor during vapor compression, and therefore represents the ability of a given compressor to pump a given amount of heat for a given volumetric flow rate of a heat transfer fluid, such as a refrigerant. In other words, given a particular compressor, a refrigerant with a higher COP will supply more cooling or heating power. One means of estimating the COP of a refrigerant under specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, for example, RCDowning, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, which is incorporated herein in its entirety by reference).

[0062] "Steam degreasing" refers to a surface cleaning process that uses solvent vapor to wash away oil and other contaminants from an article or its parts.

[0063] "Dielectric constant" means the dielectric constant measured at 20 gigahertz (GHz) at room temperature, according to ASTM D150-11 (unless other test methods, temperatures, and gigahertz are specifically mentioned).

[0064] "Dielectric strength" refers to the dielectric breakdown voltage in kV, measured according to ASTM D87-13, Procedure A, with modifications that the distance between electrodes is 2.54 mm and the rate of rise is 500 V / sec.

[0065] As used herein, the singular forms "a," "an," and "the" include multiple references unless otherwise explicitly indicated by the context.

[0066] When used herein, a numerical range indicated by an endpoint includes all numbers contained within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0067] Unless otherwise indicated, all numbers used herein and in the embodiments to express quantities or components, measured values ​​of properties, etc., should be understood in all cases to be modified by the term “approximately.” Therefore, unless otherwise indicated, the numerical parameters described in the foregoing specification and the appended list of embodiments may vary depending on the desired properties that a person skilled in the art would seek to obtain using the teachings of this disclosure. At a minimum, and without attempting to limit the application of the doctrine of equivalents to the claimed embodiments, each numerical parameter should be interpreted by applying the usual rounding technique, at least in light of the reported significant figures.

[0068] Where used herein, the phrase “any range encompassed by any two of these values ​​as endpoints” literally means that any range can be selected from any two of the values ​​enumerated prior to the phrase, regardless of whether the values ​​are in the lower or higher part of the enumeration. For example, a pair of values ​​can be selected from two lower values, two higher values, or a lower value and a higher value.

[0069] II. Synthesis from Fluoroalkenes and Fluoroalcohols The synthesis of 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane ("HFPOHFP") from HFP and HFIP is shown in Scheme 1 below.

[0070] Scheme 1 Synthesis of HFPOHFP from HFIP and HFP FIX THE SCHEME

[0071] [ka]

[0072] The synthesis of 1,1,1,2,3,3-hexafluoro-3-(2,2,2-trifluoroethoxy)propane ("TFE / HFP") from HFP and TFE is shown in Scheme 2 below.

[0073] Scheme 2 Synthesis of TFE / HFP from TFE and HFP

[0074] [ka]

[0075] The TFE / HFP compounds in this refrigerant, and / or used in accordance with this system and method, have a boiling point of about 72°C, a density of about 1.54, and a dielectric constant (less than 5.4 at 20 GHz).

[0076] In preferred embodiments, the starting materials HFP and TFE or HFIP may exist in stoichiometric ratios of 0.8:1.2 to 1.2:0.8. For example, the stoichiometric ratio of HFP to TFE may be 0.9:1.1, 1.1:0.9, or 1:1.

[0077] The reaction may preferably be carried out in an organic solvent such as dimethylformamide (DMF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF).

[0078] This reaction can preferably be catalyzed by a base such as cesium carbonate (CS2CO3), or other suitable organic or inorganic bases.

[0079] This reaction may preferably be carried out in a reactor using a level of stirring sufficient to produce a homogeneous reaction mixture. Suitable stirring can be achieved by using a mechanical stirrer or a magnetic stirring rod. The reaction vessel may be coupled to a heating medium to maintain a suitable reaction temperature. The reaction vessel may be coupled to a cooler having any suitable cooling medium to maintain a suitable reaction temperature. The reaction vessel may also be coupled to a condenser having a cooling medium for condensing solvent vapors.

[0080] The reactor may preferably be operated at a low temperature of about 0°C, 5°C, 10°C, 15°C, 20°C, or 25°C, or at a high temperature of about 30°C, 35°C, 40°C, 45°C, or 50°C, or at any temperature within a range that includes any two of these values ​​as endpoints. For example, the reaction may be carried out at a temperature of 10 to 25°C.

[0081] III. Applications of HFPOHFP and TFE / HFP fluoroethers Table 2 below outlines the physical properties of HFPOHFP in this refrigerant and / or used in accordance with this system and method.

[0082] [Table 2]

[0083] The compositions (including each of compositions 1A to 1C) may be used in a variety of applications, including but not limited to: (1) refrigerants for use in various heat transfer applications (including thermal management systems and methods), (2) aerosol propellants, (3) foaming agents, (4) gaseous dielectrics, (5) fire suppressants, (6) solvents, (7) cleaning agents, (8) power cycle working fluids, (9) electrolytes, and (10) starting materials for producing other organofluorine compounds.

[0084] The preferred refrigerants of the present invention, including each of refrigerants 1 to 8, are particularly and unexpectedly advantageous in the use and methods of heat transfer, particularly in the use and methods relating to the manufacture of electronic components, including semiconductor manufacturing. These advantages are partly due to the favorable combination of properties of the refrigerants, including viscosity and / or nonflammability, particularly in the preferred compositions including each of refrigerants 1 to 7. In certain applications, such as processes for manufacturing electronic components, where electronic components are exposed to or may be exposed to the refrigerant, a low dielectric constant is also an important property of the refrigerant.

[0085] This invention includes a refrigerant comprising refrigerants 1 to 7, the refrigerants of the present invention, which are non-flammable.

[0086] This invention includes the refrigerants of the present invention, which include refrigerants 1 to 7, the refrigerants having a dielectric constant of less than 3 at 20 GHz.

[0087] The present invention includes refrigerants 1 to 7, wherein the refrigerant has a dielectric constant of 2.5 or less at 20 GHz or less.

[0088] The present invention includes refrigerants 1 to 7, wherein the refrigerant has a dielectric constant of less than 5 at 20 GHz. (ii) It has a boiling point of about 35°C to about 80°C, (iii) is non-flammable, and (iv) has Ames-negative toxicity.

[0089] The present invention includes refrigerants 1 to 7, the refrigerants of which have a boiling point of about 35°C to about 80°C.

[0090] Referring particularly to Figure 11, a side cross-sectional view of a basic refrigerant-cooled wet etching station is illustrated. The basic operation of such a wet etching station includes providing a container 15 that holds a tank of chemical etching solution 13 for etching multiple semiconductor wafers 11. The temperature of the chemical etching solution 13 is preferably kept as uniform as possible for the purpose of maintaining the wafer surface so that the surface of the wafer 11 is uniformly etched by immersion in the tank of chemical etching solution 13 in the container 15. To maintain such a uniform temperature, multiple cooling lines 17 are installed in part of the container 15 that holds the chemical etching solution tanks 13, and as a result the cooling lines 17 are in contact with the chemical etching solution 13. During the wet etching process, the refrigerants, including each of refrigerants 1 to 8 in particular, circulate through the coolant lines 17, transporting heat from the chemical etching solution by either a sensible temperature change, a phase change, or / or a combination of a sensible temperature change and a phase change.

[0091] As mentioned above, the present invention includes methods and uses of process cooling, particularly in the manufacture of electronic components including integrated circuit formation (including etching, deposition, etc.) and microchip formation (including etching, deposition, etc.), in which the refrigerants of the present invention, including refrigerants 1 to 7, are used, or as part thereof.

[0092] The following table defines some preferred uses of the refrigerant of the present invention and methods of using the refrigerant of the present invention. Column 1 of Table 3 below identifies and defines the uses, such as Use 1, Use 2, etc., while Column 2 identifies and defines one or more of the refrigerants identified above as Refrigerant 1-8, using abbreviations such as Ref.1, Ref.2, etc. The designation "NR" is understood to mean that its component or characteristic is not required (but may be present) for the use defined in each particular row of the table.

[0093] [Table 3-1]

[0094] [Table 3-2]

[0095] [Table 3-3]

[0096] [Table 3-4]

[0097] [Table 3-5]

[0098] [Table 3-6]

[0099] In other cases, the refrigerants, including each of refrigerants 1 to 8, can be used in data centers when excess heat cannot be controlled by air cooling alone, such as during a data tsunami. In such cases where immersion cooling of electronic components, devices, and / or articles may be required, the refrigerants, including each of refrigerants 1 to 8, can be used in such immersion cooling systems to effectively remove heat while maintaining data transfer integrity, which is important in, for example, microprocessing devices and battery cooling.

[0100] Exemplary applications of the refrigerant of the present invention include applications involving immersion cooling, which are discussed below.

[0101] Heat transfer applications As mentioned above, the present invention provides various methods, processes, and uses of the refrigerants of the present invention, each of the refrigerants 1 to 8, for transferring heat from one place to another (or from one object, article, or fluid to another object, article, or fluid). For example, using the refrigerants of the present invention, each of the refrigerants 1 to 8, the temperature of components, devices, and / or articles, particularly electronic components, devices, and articles, can be maintained below a defined upper temperature limit and / or above a defined lower temperature limit. In another example, the refrigerants of the present invention, each of the refrigerants 1 to 8, can be used for capturing waste heat from industrial processes or other processes, and for energy conversion as conversion to electrical or mechanical energy.

[0102] Thermal management system and method One important category of the use of this refrigerant relates to thermal management systems and methods. Accordingly, the present invention encompasses various methods, processes, and uses of the compounds and compositions of the present invention, including the refrigerants of the present invention, each of refrigerants 1 to 8 in a thermal management system (hereinafter sometimes referred to as TMS) that operates to maintain an article or device (preferably an electronic component, device, article (including a battery)) or fluid within a specific temperature range, particularly when the article, device, or fluid is operating according to its intended purpose and / or during the manufacture of the device or article, particularly during the manufacture of an electronic device or component (such as a semiconductor wafer or integrated circuit chip). For example, a TMS can maintain the temperature of a device below a defined upper limit temperature and / or above a defined lower limit temperature, including during its processing / manufacturing.

[0103] The refrigerants of the present invention, each containing refrigerant 1 to refrigerant 8, can be used with various co-refrigerants. Preferred co-refrigerants include hexafluoroisopropyl ethyl ether, hexafluoroisopropyl methyl thioether, HFE-7000, HFE-7200, HFE-7100, HFE-7500, trans-1,2-dichloroethylene, n-pentane, cyclopentane, ethanol, perfluoro(2-methyl-3-pentanone) (Novec1230), cis-HFO-1336mzz, trans-HFO-1336mzz, HFO-1234yf, HFO-1234ze(E), HFO-1233zd(E), or HFO-1233zd(Z).

[0104] Table 4 below defines several preferred refrigerants, which are blends containing HFPOHFP and at least one co-refrigerant. The first column of the table below identifies and defines the refrigerant blends by number, such as RB1, RB2, etc., and in that column, the abbreviations COMP, CEO, and CO are used to identify the properties of the blend components identified in columns 2 and 3. In particular, the symbol COMP in column 1 indicates that the refrigerant contains HFPOHFP and the indicated co-refrigerant. The symbol CEO in column 1 means that the refrigerant is essentially made up of HFPOHFP and the specified co-refrigerant, and the symbol CO in column 1 means that the refrigerant consists of HFPOHFP and the specified co-refrigerant. The second column shows the amount of HFPOHFP required to be present in the blend. In the third column, the co-refrigerants are identified and also indicated if a specific amount of the co-refrigerant is required in the blend.

[0105] [Table 4-1]

[0106] [Table 4-2]

[0107] [Table 4-3]

[0108] [Table 4-4]

[0109] The present invention includes a refrigerant blend comprising each of RB1 to RB20, wherein the refrigerant is non-flammable.

[0110] The present invention includes a refrigerant blend comprising each of RB1 to RB20, wherein the refrigerant has a dielectric constant of less than 3 at 20 GHz.

[0111] The present invention includes a refrigerant blend comprising each of RB1 to RB20, wherein the refrigerant has a dielectric constant of less than 2.5 at 20 GHz.

[0112] The present invention comprises a refrigerant blend comprising each of RB1 to RB20, wherein the refrigerant has a dielectric constant of less than 5 at 20 GHz. (ii) It has a boiling point of about 35°C to about 80°C, (iii) it is non-flammable, and (iv) it has Ames-negative toxicity.

[0113] The present invention includes a refrigerant blend comprising each of RB1 to RB20, wherein the refrigerant has a boiling point of about 35°C to about 80°C.

[0114] As discussed above, and particularly as shown in Table 3, the refrigerants of the present invention, including each of refrigerants 1-8 and RB1-RB20, can be advantageously used in methods, apparatuses, or systems for cooling and / or heating electronic devices, and / or in methods, devices, or systems for manufacturing electronic components, devices, or articles (such as semiconductor wafers or integrated circuit chips).

[0115] Next, preferred embodiments of the thermal management method of the present invention will be considered in reference to Figure 1. An operating electronic device 10 is schematically shown as having a source of electrical energy and / or signals 20 flowing into and / or out of the device 10, and generating heat as a result of its operation based on the electrical energy and / or signals 20. The refrigerants of the present invention, each including refrigerants 1-8 and RB1-RB20, are provided in thermal contact with the operating device 10, thereby removing heat represented by the outflow arrow 30. The heat is removed from the operating electronic device by sensible heat (i.e., increasing the temperature of the liquid) added to the liquid thermal management fluid of the present invention, or by causing a phase change (i.e., vaporizing the liquid) in the thermal management fluid, or by a combination of these. In a preferred embodiment, the method provides a supply of the refrigerants of the present invention, each including refrigerants 1-8 and RB1-RB20, to the device 10, and as a result, the flow of heat from the device 10 through the refrigerants 30 of the present invention maintains the operating electrical device within a preferred operating temperature range, or within a preferred operating temperature range. In a preferred embodiment, the preferred operating temperature range of the electrical device is about 70°C to about 150°C, more preferably about 70°C to about 120°C, and the flow of heat 30 from the device 10 through the refrigerant of the present invention, which includes refrigerants 1 to 8 and RB1 to RB20, keeps the operating electrical device within such preferred temperature range, or maintains it within such preferred range. Preferably, the refrigerant 30 of the present invention, having absorbed heat from the device, comes into thermal contact with a heat sink schematically represented as 40, which is at a temperature below the temperature of the heat transfer fluid 30, thereby transferring the heat generated by the device 10 to the heat sink 40. In this way, the thermally depleted refrigerant 50 is returned to the electronic device 10, allowing the cooling cycle to be repeated.

[0116] In a preferred embodiment of the method of the present invention, the step of removing heat through the refrigerant of the present invention, each comprising refrigerants 1-8 and RB1-RB20, includes evaporating the refrigerant using heat generated by the operation of an electronic device, and the step of transferring that heat from the refrigerant to a heat sink includes condensing the refrigerant by releasing the heat to the heat sink. In such a method, during the evaporation step, the temperature of the refrigerant of the present invention, each comprising refrigerants 1-8 and RB1-RB20, is preferably above 50°C, preferably above about 55°C, preferably between about 55°C and about 85°C, or preferably between about 65°C and about 75°C. The applicants have found that the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, provide excellent performance in such a method, while also enabling the provision of required cooling using relatively low-cost, lightweight, and reliable equipment, as will be further described in relation to the specific embodiment described below in connection with Figure 2A.

[0117] In a more preferred embodiment of the method of the present invention, the step of removing heat via the refrigerants of the present invention, each of the refrigerants 1-8 and RB1-RB20, includes the steps of using the heat generated by the operation of the electronic device to add sensible heat to the refrigerant (for example, raising the liquid temperature to approximately 70°C or less at near atmospheric pressure, i.e., the fluid does not need to be in a high-pressure vessel or vessel), and transferring that heat from the refrigerant to a heat sink, thereby reducing the liquid temperature by releasing heat to the heat sink. The cooled liquid is then returned to thermal contact with the electrical device to repeat the cycle. In a preferred embodiment, the temperature of the refrigerant transferring heat to the heat sink is above approximately 40°C, preferably above approximately 55°C, preferably in the range of approximately 45°C to approximately 70°C, or preferably in the range of approximately 45°C to approximately 65°C, preferably at a pressure of approximately atmospheric pressure. The applicants have found that the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, provide excellent performance in such a manner, while also enabling the provision of required cooling using relatively low-cost, lightweight, and reliable equipment, as will be further described in relation to the specific embodiments shown below in connection with Figure 2B.

[0118] Those skilled in the art will understand that the present invention includes systems and methods that utilize both sensible heat transfer and phase-change heat transfer, as described above.

[0119] Herein, a specific method according to the present invention is described in reference to Figures 2A and 2B, in which the electronic device 10 is housed in a suitable container 12, preferably a sealed container, and is in direct contact with the liquid refrigerant 11A of the present invention (circularly shown in gray shading), which contains each of the refrigerants 1-8 and RB1-RB20, and preferably is completely immersed in the liquid refrigerant of the present invention. For convenience, such cooling methods, devices, and systems may be referred to herein as “immersion cooling” methods, devices, and systems.

[0120] In immersion cooling methods, devices, and systems used to cool electrical devices or components, the operating electronic device 10 has a source of electrical energy and / or signals 20 that flows into and / or out of the container 12 and into and / or out of the device 10, and generates heat as a result of operation based on the electrical energy and / or signals 20. As will be understood by those skilled in the art, the fluid must not only provide all the other properties mentioned above, but also be able to provide all the other properties mentioned above while in close contact with the operating electronic device, i.e., an electronic device with a flow of current / signals, so finding a refrigerant that can perform effectively in such an application is a critical challenge. It will be understood that many fluids that may otherwise be promising for use in such an application would either short-circuit and degrade the device (degrading the cooling effect over time and / or degrading the operational stability of the device) when exposed to the conditions resulting from the operation of the electronic device, or have some other properties that are detrimental to the operation when in contact with the operating electronic device.

[0121] In contrast, the thermal management method of the present invention yields superior and unexpected results by providing the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20, in direct thermal and physical contact with the device 10 while the device 10 is operating. The heat of this operation is safely and effectively transferred to the refrigerant 11A by (a) vaporizing the liquid phase of the fluid refrigerant to form vapor 11B, or (b) raising the temperature of the liquid refrigerant 11A, or (c) a combination of (a) and (b).

[0122] If the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20 respectively, are single-phase liquids, they will remain liquid even when heated by the heat-generating components. Therefore, the refrigerants can come into contact with the heat-generating components, resulting in the removal of heat from the heat-generating components and the generation of a higher-temperature refrigerant. The refrigerants are then transferred to a secondary cooling loop, such as a radiator or another cooling system. An example of such a system is illustrated in Figure 2, in which the refrigerant enters a battery pack housing containing several cells, removes heat from the battery pack, and exits the housing.

[0123] When the refrigerant of the present invention, each containing refrigerants 1-8 and RB1-RB20, is present in two phases, the heat-generating component comes into thermal contact with the refrigerant of the present invention, each containing refrigerants 1-8 and RB1-RB20, transferring heat to the refrigerant, which then boils. The refrigerant is then condensed. An example of such a system is in which the heat-generating component is immersed in the refrigerant of the present invention, each containing refrigerants 1-8 and RB1-RB20, and an external cooling circuit condenses the boiling fluid into a liquid state.

[0124] In the case of the phase-change heat transfer system of the present invention, Figure 2A is referred to herein. In such operation, the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20 respectively, evaporate, and heat is carried away from the device 10 as the vapor rises through the remaining refrigerant liquid in the container 12. The refrigerant vapor 11B then releases the absorbed heat into a heat sink 40, which may be a closed heat sink 40A and / or an external heat sink 40B. Examples of heat sinks inside the container 12 include condenser coils 30A and 30B having a circulating fluid, such as water, at a temperature below the condensation temperature of the refrigerant vapor. An example of a heat sink outside the container 12 is to pass relatively cool ambient air over the container 12 (in this case preferably including cooling fins, etc.), which would serve to condense the heat transfer vapor 11B on the inner surface of the container. As a result of this condensation, the liquid refrigerant is returned to the pool of liquid fluid 11A into which the device 10 remains immersed during operation.

[0125] In the case of the sensible heat transfer system of the present invention, Figure 2B is referred to herein. In such operation, as the temperature of the liquid 11A containing the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20 respectively, increases when receiving heat generated by a device immersed, preferably substantially completely immersed, in the refrigerant 11A of the present invention, heat is carried away from the device. The hotter refrigerant liquid 11A then releases the heat it has absorbed into a heat sink 40, which may be a closed heat sink 40A and / or an external heat sink 40B. An example of a heat sink inside the container 12 is cooling coils 30A and 30B having a circulating fluid, such as water, at a temperature below the temperature of the heated liquid. An example of a heat sink outside the container 12 is removing the heated liquid 11A from the container through a conduit 45, which is thermally contacted with a cold fluid, such as relatively cold ambient air or cooled water or refrigerant, which functions to lower the temperature of the liquid. The cooled liquid is then returned through a conduit 46.

[0126] In certain embodiments involving thermal management of a battery used in an electric vehicle, optionally, but preferably, the thermal management system includes a heating element capable of heating the refrigerant of the present invention, which includes each of the refrigerants 1-8 and RB1-RB20, such as an electric heating element 60 which is also immersed in the refrigerant. As those skilled in the art will understand, the battery in an electric vehicle (corresponding to the operating electronic device 10 in Figures 2A and 2B) can reach relatively low temperatures while parked outdoors in many geographical locations during the winter months, and frequently, such low-temperature conditions are undesirable for battery operation. Therefore, the thermal management system of the present invention may include a sensor and control module (not shown) that turns on the heating element when the battery temperature falls below a predetermined level. In such a case, the heater 60 will be activated and the refrigerant liquid 11A will be heated, thereby transferring this heat to the electronic device 10 until it reaches a minimum temperature. Thereafter, during operation, the refrigerant of the present invention, which includes each of the refrigerants 1-8 and RB1-RB20, will perform the cooling function as described above.

[0127] For the purposes of the present invention, the refrigerants of the present invention, each of the refrigerants 1 to 8 and RB1 to RB20, can come into direct contact with the heat-generating components or come into indirect contact with the heat-generating components.

[0128] When the refrigerants of the present invention, including each of refrigerants 1-8 and RB1-RB20, are indirectly in contact with heat-generating components, the refrigerant fluid may be used in a closed system within an electronic device, which may include at least two heat exchangers. When cooling heat-generating components using the refrigerants of the present invention, including each of refrigerants 1-8 and RB1-RB20, heat can typically be transferred from the components to the refrigerant through heat exchangers in contact with at least a portion of the components, or the heat can be transferred to circulating air that can conduct heat to heat exchangers in thermal contact with the refrigerant.

[0129] In a particularly preferred feature of the present invention, the refrigerants of the present invention, including each of refrigerants 1-8 and RB1-RB20, are in direct contact with the heat-generating components. In particular, the heat-generating components are completely or partially immersed in the refrigerant. Preferably, the heat-generating components are completely immersed in the refrigerant of the present invention, including each of refrigerants 1-8 and RB1-RB20. The refrigerant may then be circulated to a heat exchanger as a heated fluid or as vapor, which takes heat from the fluid or vapor and transfers that heat to the external environment via a heat sink such as ambient air or water cooled by ambient air or other means. After this heat transfer, the cooled refrigerant (cooled or condensed) is returned to the system and recirculated to cool the heat-generating components.

[0130] The conductivity and / or dielectric strength of the refrigerant are important when the fluid is in direct contact with the electronic components of an electronic device (such as direct immersion cooling), or when the refrigerant leaks from the cooling loop or spills during maintenance and comes into contact with an electrical circuit. Therefore, the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20, are preferably electrically insulating thermal management fluids.

[0131] The refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, can be recirculated passively or actively within the device, for example, by using mechanical devices such as pumps. A preferred feature of the present invention is that the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, are passively recirculated within the device.

[0132] A passive recirculation system typically works by transferring heat from the exothermic components to the refrigerant until the refrigerant vaporizes, allowing the heated vapor to move to a heat exchange surface, where it transfers its heat to the heat exchanger surface, condensing back into a liquid. It will be understood that the heat exchange surface may be part of a separate heat exchange unit and / or integrated with a container, for example, as described above in relation to Figure 2.

[0133] The condensed liquid then preferably returns completely passively to the refrigerant in contact with the heat-generating components by gravity and / or a suction structure. Thus, in a preferred feature of the present invention, the step of transferring heat from the heat-generating components to the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20 respectively, vaporizes the heat-managed fluid.

[0134] Examples of passive recirculation systems include heat pipes or thermal siphons. Such systems utilize gravity to passively recirculate the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20, respectively. In such systems, the refrigerants are heated by the exothermic components to become heated refrigerants with lower density and higher buoyancy. This heated refrigerant moves to a storage container, such as a tank, where the refrigerants cool and condense. The cooled refrigerants then flow back to the heat source.

[0135] Cooling of electrical devices This disclosure includes using the refrigerants of the present invention, each of which includes refrigerants 1 to 8 and RB1 to RB20, to cool and optionally heat electronic devices that manufacture or contain components that are heat-generating components. Heat-generating components may be any components that include electronic elements that generate heat as part of their operation. For the purposes of the present invention, heat-generating components include, but are not limited to, microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, power distribution switchgears, power transformers, circuit boards, multichip modules, packaged or unpackaged semiconductor devices, semiconductor integrated circuits, fuel cells, lasers (conventional or laser diodes), light-emitting diodes (LEDs), and semiconductor integrated circuits (ICs), electrochemical cells, power transistors, resistors, and electroluminescent elements, such as electrochemical cells used in high-power applications, such as hybrid or electric vehicles.

[0136] For the purposes of the present invention, electronic devices include, but are not limited to, personal computers, microprocessors, servers, mobile phones, tablets, digital home appliances (e.g., televisions, media players, game consoles, etc.), personal digital assistants, data centers, both stationary and vehicle-mounted batteries including lithium-ion batteries, hybrid or electric vehicles, wind turbines, train engines, or other batteries used in generators. Preferably, the electronic device is a hybrid or electric vehicle.

[0137] The present invention further relates to an electronic device comprising the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20. For the purposes of the present invention, the refrigerants are provided for cooling and / or heating the electronic device.

[0138] The present invention further relates to an electronic device comprising a heat-generating component for cooling and optionally heating the electronic device, and a refrigerant of the present invention, each of which comprises refrigerants 1 to 8 and RB1 to RB20.

[0139] The present invention further relates to an electronic device comprising a heat-generating component, a heat exchanger, a pump, and a refrigerant of the present invention, each of which includes refrigerants 1 to 8 and RB1 to RB20. For the purposes of the present invention, the electronic device may include, but is not limited to, personal computers, microprocessors, servers, mobile phones, tablets, digital home appliances (e.g., televisions, media players, game consoles, etc.), personal digital assistants, data centers, hybrid or electric vehicles, both stationary and on-board batteries, electric drive motors, fuel cells (e.g., hydrogen fuel cells), and generators. Preferably, the electronic device is located in a hybrid or electric vehicle, or a wind turbine, or a train.

[0140] For the purposes of the present invention, the heat-generating component may be any electrical component that generates heat during operation or during its manufacture, and such electrical component may include an electronic component that generates heat at a high level of thermal flux and / or is exposed to such heat. Exemplary components that can be cooled during operation and / or during manufacture using the refrigerants of the present invention, including refrigerants 1 to 8 and RB1 to RB20, include semiconductor integrated circuits (ICs), electrochemical cells, power transistors, resistors, and electroluminescent elements, such as microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, power distribution switchgears, power transformers, printed circuit boards (PCBs), multi-chip modules, packaged or unpackaged semiconductor devices, semiconductor integrated circuits, fuel cells, lasers (conventional lasers or laser diodes), light-emitting diodes (LEDs), and electrochemical cells used in high-power applications, such as hybrid or electric vehicles.

[0141] Lithium-ion battery cooling system An example of a thermal management method useful for cooling lithium-ion batteries, including the use of refrigerants of the present invention, each of which includes refrigerants 1-8 and RB1-RB20, is described here with reference to Figure 8, in such a method including heat transfer method 1. A vehicle battery pack having an integrated liquid cooling system 10 including a module 12 formed of a container 14 having an internal space 16 for supporting a battery assembly 18. The container 14 is a closed and sealed container 14 for forming the self-integrated liquid cooling system 10. The battery assembly 18 includes a plurality of battery cells 20, such as a plurality of lithium-ion (Li-ion) batteries for use in a hybrid vehicle. In another embodiment, the plurality of battery cells 20 are Li-ion batteries for use in a battery electric vehicle (BEV). Additional batteries for use with other motorized vehicles may be provided in the liquid cooling system 10 of the present invention, and each battery cell contains an active material for generating electricity from an electrochemical reaction in the internal space 16 of the container 14. Preferably, the battery cells 20 are stacked to form a battery cell stack 22. In the embodiment shown, the gap 24 between each battery cell 20 is 0.25 to 0.50 mm, forming a fluid channel 26 between each battery cell 20. In another embodiment, the gap 24 may be less than 0.25 mm. It is understood that other gap sizes may be used as desired.

[0142] The composition of the present invention, comprising composition 1, and the refrigerants of the present invention, comprising each of refrigerants 1-8 and RB1-RB20, are disposed within the internal space 16 of the container 14, and the indicated fluid level is such that the battery assembly 18 is completely immersed in the composition / refrigerants of the present invention. The composition of the present invention, comprising composition 1, and the refrigerants of the present invention, comprising each of refrigerants 1-8 and RB1-RB20, are in contact with the battery cell 20 through fluid channels 26 formed by gaps 24.

[0143] The heating element 34 is located in the base region 36 of the container 14. The heating element 34 shown is an electronic heating element. It is understood that other types of heating elements may be used. The heating element 34 is shown as a single element. However, multiple heating elements 34, such as heating plates, may be provided.

[0144] The cooling element 38 is located in the upper region 40 of the container 14. The cooling element 38 may be a chilled water condenser having an inlet 42 and an outlet 44 that extend beyond the wall of the sealed container 14 for supplying and discharging water for the cooling element 38. In another embodiment, the cooling element 38 may be a chilled water plate. In yet another embodiment, the cooling element 38 may be a thin aluminum heat sink having external chilled water flowing through the cooling element 38. The cooling element 38 may be graphite foil impregnated with an electrically nonconductive polymer. The cooling element may also be formed from copper.

[0145] In the embodiments shown, arrows "A" and "B" indicate the flow 28 of the refrigerants of the present invention, including composition 1, and each of the refrigerants 1-8 and RB1-RB20. When each battery cell 20 is heated by the heating element 34, the fluid 28 containing the refrigerants of the present invention, including composition 1, and each of the refrigerants 1-8 and RB1-RB20 are exposed to the front surface region 30 and rear surface region 32 of the battery cell 20 and will boil. The heated coolant 28 rises and flows to the top of the battery cell stack 22 and is cooled by the cooling element 38. The cooled coolant 28 generally returns to the base region 36 according to either coolant path "A" or "B". The coolant 28 will tend to follow path "A" if the general position of the coolant 28 at the moment of boiling is within the fluid channel 26 of the battery cell 20 in the central region and toward the side surface 50 of the container 14. Similarly, if the general position of the dielectric coolant 28 at the moment of boiling is within the fluid channel 26 of the battery cell 20 in the central region and toward the opposing side surface 52 of the container 14, the dielectric coolant 28 will tend to follow the flow path "B".

[0146] The coolant temperature sensor 46 is located on or near the cooling element 38. In the shown embodiment, the temperature sensor 46 is located within the region of the outlet 44 of the cooling element 38 and measures the temperature of the dielectric coolant 28 of the present invention at the point of exposure to the cooling element. The temperature sensor 46 may be located anywhere within the battery cell stack 22, if desired.

[0147] A coolant level sensor 48 is also provided, located near the upper region 40 of the container 14, to measure the fluid level of the dielectric coolant 28 in the container 14, which contains the composition of the present invention, including composition 1, and the refrigerants of the present invention, including each of refrigerants 1-8 and RB1-RB20, thereby ensuring complete immersion of the battery assembly 18 in the dielectric coolant 28.

[0148] Cooling and heating of heat pipes Herein, an example of the heat transfer method of the present invention using heat pipes is described with reference to Figure 10, which is a specific example of heat pipes in an energy storage assembly 1 according to one exemplary embodiment of the present invention. The energy storage assembly 1 may be part of an automobile 12, in particular a hybrid or electric vehicle, and is provided on the side of the automobile to supply power to an electrical consuming device, such as an electric drive unit (not shown). The energy storage assembly 1 includes a plurality of electrical energy storage units. 2. The electrical energy storage units 2 are electrically connected via electrical connection elements (not shown), in particular in the form of conductive rails or conductor rails ("busbars"), i.e., connected in series or in parallel. The electrical connection elements are in contact with corresponding electrical connectors (not shown) herein, which are located on the respective exposed outer wall areas of the corresponding energy storage housings (not shown) of the energy storage units 2 arranged in parallel adjacent to each other, thereby forming an energy storage stack ("stack"). Plate-shaped spacer elements 3 are respectively placed between the energy storage units 2 to separate them and at the same time have thermal conductivity properties. Therefore, the spacer element 3 provides, on the one hand, a gap between directly adjacent energy storage units 2 so that they do not come into electrical or mechanical contact with each other. On the other hand, the spacer element 3 acts as a thermal conductor, as a result of their thermal conductivity, for the purpose of cooling the energy storage units 2 or energy storage assembly 1 by dissipating heat, particularly from the energy storage units 2 that are in contact with each other, or for the purpose of heating the energy storage units 2 or energy storage assembly 1 by supplying heat, particularly to the energy storage units 2 that are in contact with each other. The heat pipe 4 of the first heat pipe assembly 5 and the heat pipe 6 of the second heat pipe assembly 7 are provided. Therefore, the heat pipes 4 and 6 extend along this side surface of the energy storage stack and are thermally coupled to the spacer element 3, respectively. Thus, the spacer element 3 forms thermal bridges, on the one hand, between the heat pipe 4 of the first heat pipe assembly 5 and the heat pipe 6 of the second heat pipe assembly 7, and on the other hand, between the energy storage units 2.Each heat pipe 4 of the first heat pipe assembly 5 is positioned and aligned such that it is thermally coupled to its respective evaporation zone, and within this zone, the contained refrigerant of the present invention, including each of refrigerants 1-8 and RB1-RB20, can evaporate relative to the spacer element 3. Therefore, the heat required for the evaporation of the refrigerant of the present invention (heat of evaporation) is removed from the spacer element 3 or from the energy storage unit 2 via the spacer element 3. Thus, the energy storage unit 2, including the energy storage assembly 1, can be cooled via the heat pipes 4 of the first heat pipe assembly 5. Furthermore, each condensation zone of the heat pipe 4 of the first heat pipe assembly 5 (where the contained gaseous refrigerant of the present invention, including each of refrigerants 1-8 and RB1-RB20, can be condensed) is thermally coupled to a heat sink 8 in the form of an automotive-side heat exchanger. Therefore, the heat generated during condensation of the present invention (heat of condensation) can be transferred to the heat sink 8. The heat exchanger can be part of the energy storage assembly 1, that is, it can belong to the energy storage assembly 1 or be associated with the energy storage assembly 1. Each heat pipe 6 of the second heat pipe assembly 7 is positioned and aligned with respect to the spacer element 3, such as by being thermally coupled to its respective condensation zone, in which the contained gaseous refrigerant of the present invention can be condensed. Therefore, heat (heat of condensation) can be transferred to or via the spacer element 3 to the energy storage unit 2 during the condensation of the refrigerant of the present invention. Thus, the energy storage unit 2 and the energy storage assembly 1 can be heated via the heat pipes 6 of the second heat pipe assembly 7. In addition, each evaporation zone of the heat pipe 6 of the second heat pipe assembly 7 (in which the contained refrigerant of the present invention can be evaporated) is thermally coupled to a heat source 9, i.e., a functional component associated with the energy storage assembly 1, i.e., a heat source 9 in the form of, for example, a charger or control device or control electronic equipment. Thus, the heat (heat of evaporation) required for the evaporation of the refrigerant can be removed from the heat source 9. Thus, the functional component can be cooled via the heat pipes 6 of the second heat pipe assembly 7.The two heat pipe assemblies 5 and 7 and their associated heat pipes 4 and 6 enable the implementation of a temperature control device for controlling the temperature of the energy storage section 2 of the energy storage assembly 1, i.e., for heating or cooling. Useful heat pipes according to the present invention include both gravity return heat pipes, capillary return heat pipes, and gravity / capillary return heat pipes.

[0149] Organic Rankine Cycle System When the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20, are used in an organic Rankine cycle, they may be referred to as working fluids.

[0150] Therefore, this working fluid corresponds to a refrigerant as considered in this application. All preferred characteristics of a heat transfer fluid apply to the working fluid described herein.

[0151] The Rankine cycle system is known to be a simple and reliable means of converting thermal energy into mechanical energy in the form of shaft power. In industrial environments, it may be possible to use flammable working fluids such as toluene and pentane, especially when the industrial environment already has large quantities of flammable materials in operation or storage on site. However, in cases where the risks associated with the use of flammable and / or toxic working fluids are unacceptable, such as in power generation in densely populated areas or near buildings, it is necessary, or at least highly desirable, to use non-flammable and / or non-toxic refrigerants as working fluids. There is also a movement within the industry to make these materials environmentally acceptable from a GWP perspective.

[0152] The process for recovering waste heat in the organic Rankine cycle according to the present invention preferably involves pumping a liquid-phase working fluid of the present invention, which includes the refrigerants of the present invention, each of which includes refrigerants 1 to 8 and RB1 to RB20, through a boiler, where an external (waste) heat source, such as a process flow, heats the working fluid and evaporates it to saturated steam or superheated steam. This steam expands through a turbine, and the waste heat energy is converted into mechanical energy.

[0153] Next, the gaseous working fluid is condensed into a liquid and pumped back to the boiler to repeat the heat extraction cycle.

[0154] Referring to Figure 4, in the exemplary organic Rankine cycle system 70, the working fluid of the present invention, which includes the refrigerants of the present invention, each of which includes refrigerants 1-8 and RB1-RB20, is circulated between the evaporator 71 and the condenser 75, with a pump 72 and an expansion device 74 functionally arranged between them. In the illustrated embodiment, the external flow of the fluid is directed to the evaporator 71 via an external warm conduit 76. The external warm conduit 76 can carry the fluid from a warm heat source such as industrial processes (e.g., power generation), flue gas, exhaust gas, or waste heat from a geothermal source.

[0155] The evaporator 71 is preferably configured as a heat exchanger, which may include, for example, a series of thermally connected but fluidly isolated tubes that carry fluid from a warm conduit 76 and fluid from a working fluid conduit 77B, respectively. Thus, the evaporator 71 facilitates the transfer of heat QIN from the warm fluid arriving from the external warm conduit 76 to the relatively cooler (e.g., "low-temperature") working fluid arriving from the expansion device 74 via the working fluid conduit 77B.

[0156] Therefore, the working fluid of the present invention, which contains the fluoroether of the present invention, is heated by the absorption of heat QIN and exits the evaporator 71, then moves through the working fluid conduit 78A to the pump 72. The pump 72 pressurizes the working fluid, thereby further heating the fluid through an external energy input (e.g., electricity). The resulting "hot" fluid moves through conduit 78B and optionally, through the regenerator 73 as described below, to the input of the condenser 75.

[0157] The condenser 75 is configured as a heat exchanger similar to the evaporator 71 and may include, for example, a series of thermally connected but fluidly isolated tubes that carry fluid from a cold conduit 79 and fluid from a working fluid conduit 78B, respectively. The condenser 75 facilitates the transfer of heat QOUT from the external cold conduit 79 to the cold fluid arriving at the relatively warmer (e.g., "high temperature") working fluid of the present invention, which contains the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20, respectively, arriving from the pump 72 via the working fluid conduit 78B.

[0158] The working fluid of the present invention, including refrigerants 1-8 and RB1-RB20 respectively, which exits the condenser 75 and is subsequently cooled by the heat loss QOUT, then moves through the working fluid conduit 77A to the expansion device 74. The expansion device 74 allows the working fluid to expand, thereby further cooling the fluid. At this stage, the fluid of the present invention, including the fluoroether of the present invention, can perform work, for example, by driving a turbine. The resulting "low-temperature" fluid moves through conduit 77B and optionally through regenerator 73, as described below, to the input of evaporator 71, where a new cycle begins.

[0159] Therefore, the working fluid conduits 77A, 77B, 78A, and 78B define a closed loop, and as a result, the working fluid contained within them can be reused indefinitely or until maintenance of the conduit is required.

[0160] In the illustrated embodiment, the regenerator 73 may be functionally positioned between the evaporator 71 and the condenser 75. The regenerator 73 allows the “high-temperature” working fluid of the present invention, containing the fluoroether of the present invention, discharged from the pump 72, and the “low-temperature” working fluid flowing out from the expansion device 74 to exchange some heat, with a potential time lag between the accumulation of heat from the high-temperature working fluid and the release of that heat to the low-temperature working fluid. In some applications, this can increase the overall thermal efficiency of the Rankine cycle system 70.

[0161] The present invention also provides a process for converting thermal energy into mechanical energy in a Rankine cycle, the method comprising: i) vaporizing a working fluid of the present invention, which includes each of the refrigerants of the present invention, which include refrigerants 1-8 and RB1-RB20, with a heat source and expanding the resulting vapor; and then ii) cooling the working fluid with a heat sink to condense the vapor, wherein the working fluid is a refrigerant of the present invention, which includes each of the refrigerants 1-8 and RB1-RB20.

[0162] Mechanical work can be transmitted to electrical devices such as generators to produce electricity.

[0163] The heat source may be selected from, for example, industrial waste heat, solar energy, geothermal hot water, low-pressure steam, distributed power generation equipment utilizing fuel cells, prime movers, or internal combustion engines. Low-pressure steam is preferably low-pressure geothermal steam or provided by a power plant powered by fossil fuels.

[0164] The heat source is preferably provided by a thermal energy source selected from industrial waste heat or an internal combustion engine.

[0165] It will be understood that while the heat source temperature can vary widely, for example, from approximately 90°C to over 800°C, it can also depend on a multitude of factors, including geography and season, for certain combustion gases and some fuel cells.

[0166] For example, systems based on sources such as wastewater or low-pressure steam from plastic manufacturing plants and / or chemical plants or other industrial plants, petroleum refineries and related forms, as well as geothermal sources, may have source temperatures as low as approximately 175°C or below, or approximately 100°C or below, and in some cases as low as approximately 90°C, or even as low as approximately 80°C. Gaseous heat sources such as exhaust gas from combustion processes where subsequent processing to remove particulate matter and / or corrosive species results in low temperatures, or from any heat source, may also have source temperatures as low as approximately 200°C or below, approximately 175°C or below, approximately 130°C or below, approximately 120°C or below, approximately 100°C or below, and in some cases as low as approximately 90°C, or even as low as approximately 80°C.

[0167] However, in some applications, it is preferable that the heat source has a temperature of at least about 200°C, for example, between about 200°C and about 400°C.

[0168] In an alternative preferred embodiment, the heat source has a temperature of 400°C to 800°C, more preferably 400°C to 600°C.

[0169] heat pump The refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, can be used in high-temperature heat pump systems.

[0170] Referring to Figure 5, in one exemplary heat pump system, a compressor 80, such as a rotary, piston, screw, or scroll compressor, compresses the refrigerants of the present invention, each containing refrigerants 1-8 and RB1-RB20, which are then carried to a condenser 82 to release heat QOUT to a first position, then pass the refrigerant through an expansion device 84 to reduce the refrigerant pressure, and subsequently pass the refrigerant through an evaporator 86 to absorb heat QIN from a second position. The refrigerant is then returned to the compressor 80 for compression.

[0171] The present invention provides a method for heating a fluid or object using a high-temperature heat pump, the method comprising (a) condensing or heating a refrigerant of the present invention, each of the refrigerants 1-8 and RB1-RB20, around a fluid in an object, and (b) evaporating the refrigerant.

[0172] Examples of high-temperature heat pumps include heat pump tumble dryers or industrial heat pumps. It will be understood that a heat pump may be equipped with a suction line / liquid line heat exchanger (SL-LL HX). A "high-temperature heat pump" means a heat pump capable of generating a temperature of at least about 80°C, preferably at least about 90°C, preferably at least about 100°C, and more preferably at least about 110°C.

[0173] Secondary Loop System The refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, can be used as secondary refrigerant fluids in a secondary loop system.

[0174] The secondary loop system includes a primary vapor compression system loop that uses a primary refrigerant, the vapor of which cools the fluid in the secondary loop. A secondary refrigerant fluid, containing the refrigerants of the present invention, each of which includes refrigerants 1-8 and RB1-RB20, then provides the cooling required for the application. Since the fluid in such a loop is potentially exposed to humans near the cooled space, the secondary refrigerant fluid must preferably be non-flammable and low-toxicity. In other words, the refrigerants of the present invention, each of which includes refrigerants 1-8 and RB1-RB20, can be used as the “secondary refrigerant fluid” in a secondary loop system.

[0175] Referring to Figure 6, one exemplary secondary loop system includes a primary loop 90 and a secondary loop 92. In the primary loop 90, a compressor 94, such as a rotary, piston, screw, or scroll compressor, compresses the primary refrigerant, which is then carried to a condenser 96 to release heat QOUT to a first position, and subsequently the primary refrigerant is passed through an expansion device 98 to reduce the refrigerant pressure, and subsequently the primary refrigerant is passed through a refrigerant / secondary fluid heat exchanger 100 to exchange heat QIN with a secondary fluid containing the fluoroether of the present invention, and the secondary fluid is pumped through the secondary loop 92 via a pump 102 to a secondary loop heat exchanger 104 to exchange heat with further positions, for example, to provide cooling to further positions by absorbing heat QIN-S.

[0176] The primary fluid used in the primary loop (the vapor compression cycle of the loop, the external / outdoor portion) may be selected from, but is not limited to, HFO-1234ze(E), HFO-1234yf, propane, R455A, R32, R466A, R44B, R290, R717, R452B, R448A, and R449A, preferably HFO-1234ze(E), HFO-1234yf, or propane.

[0177] A secondary loop system can be used for cooling or air conditioning applications; that is, a secondary loop system can be a secondary loop cooling system or a secondary loop air conditioning system.

[0178] Examples of cooling systems that may include a secondary loop cooling system containing the secondary refrigerant of the present invention, which includes the fluoroether of the present invention, include low-temperature cooling systems, medium-temperature cooling systems, commercial refrigerators, commercial freezers, industrial freezers, industrial refrigerators, and chillers.

[0179] Examples of air conditioning systems that may utilize the secondary loop air conditioning system of the present invention, which includes the fluoroether refrigerant of the present invention, include mobile air conditioning systems and stationary air conditioning systems. Mobile air conditioning systems include air conditioning for road vehicles such as automobiles, trucks, and buses, as well as air conditioning for boats and trains. For example, when the vehicle includes a battery or power source.

[0180] Examples of stationary air conditioning systems that may utilize a secondary loop air conditioning system using the refrigerant of the present invention, including the fluoroether of the present invention, include chillers, particularly positive displacement chillers, especially air-cooled or water-cooled direct expansion chillers, which are either modular or conventionally packaged as standalone units; residential air conditioning systems, particularly duct-split or ductless-split air conditioning systems; residential heat pumps; residential air-water heat pump / hot water systems; industrial air conditioning systems; commercial air conditioning systems, particularly packaged rooftop units; and variable refrigerant flow (VRF) systems; and commercial air-source, water-source, or soil-source heat pump systems.

[0181] A particularly preferred heat transfer system according to the present invention is an automotive air conditioning system comprising a vapor compression system (primary loop) and a secondary loop air conditioning system, wherein the primary loop contains HFO-1234yf as a refrigerant, and the secondary loop contains a refrigerant or heat transfer composition of the present invention, which includes the fluoroether of the present invention. In particular, the secondary loop may be used to cool components within an automobile engine, such as a battery.

[0182] It will be understood that secondary loop air conditioning or cooling systems may be equipped with suction line / liquid line heat exchangers (SL-LL HX).

[0183] The heat transfer fluid or heat transfer composition of the present invention, which may include a secondary loop air conditioning system utilizing the refrigerant of the present invention containing the fluoroether of the present invention, can be used as a substitute for existing fluids.

[0184] The present invention includes a method for replacing an existing heat transfer fluid in a heat transfer system, the method comprising (a) removing at least a portion of the existing heat transfer fluid from the system, and (b) introducing the heat transfer fluid of the present invention into the system. Step (a) may include removing at least about 5% by weight, at least about 10% by weight, at least about 15% by weight, at least about 50% by weight, at least about 70% by weight, at least about 90% by weight, at least about 95% by weight, at least about 99% by weight, or at least about 99.5% by weight, or substantially all, of the existing heat transfer fluid from the system prior to step (b).

[0185] This method may optionally include a step of flushing the system with a solvent after performing step (a) and before performing step (b).

[0186] For the purposes of the present invention, the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, can be used to replace existing fluids in electronic devices, organic Rankine cycles, high-temperature heat pumps, or secondary loops.

[0187] For example, the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, can be used as substitutes for existing fluids such as HFC-4310mee, HFE-7100, and HFE-7200. Alternatively, water and glycol can be replaced using the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20. The substitutes may be in existing systems or in new systems designed to function with existing fluids. Alternatively, the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, can be used in applications where existing refrigerants were previously used. Alternatively, existing refrigerants can be retrofitted to existing systems using the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20.

[0188] Alternatively, the refrigerants of the present invention, including refrigerants 1-8 and RB1-RB20 respectively, can be used in new systems designed to function with existing refrigerants.

[0189] The present invention provides a method for replacing an existing refrigerant in a heat transfer system, the method comprising (a) removing at least a portion of the existing refrigerant from the system, and (b) introducing the refrigerants of the present invention, each comprising refrigerants 1-8 and RB1-RB20, into the system. The existing refrigerants may be selected from, for example, HFC-4310mee, HFE-7100, and HFE-7200.

[0190] Step (a) may include removing at least about 5% by weight, at least about 10% by weight, at least about 15% by weight, at least about 50% by weight, at least about 70% by weight, at least about 90% by weight, at least about 95% by weight, at least about 99% by weight, or at least about 99.5% by weight of the existing refrigerant from the system prior to step (b).

[0191] This method may optionally include a step of flushing the system with a solvent after performing step (a) and before performing step (b).

[0192] Use, methods, and systems of solvents and washing. The present invention provides solvation methods. Such methods include cleaning methods using the compositions of the present invention, which include composition 1, etching methods in general, carrier solvent applications (including, for example, those related to the coating of medical devices heparin and PTFE, coating applications, lubricant deposition, silicone deposition, and other coatings).

[0193] With respect to cleaning methods, all such methods are included within the scope of the present invention. A preferred cleaning method is vapor degreasing by bringing an article, device, or component thereof into contact with the composition of the present invention, which comprises composition 1. A wide variety of contaminants can be removed from a wide variety of articles, devices, and components. Examples of contaminants that can be removed using the composition of the present invention, which comprises the fluoroether of the present invention, include, for example, diesel fuel, medium oil, fluorinated lubricants, greases, and silicones and waxes. Examples of articles, devices, and components that can be cleaned using the composition of the present invention, which comprises composition 1, include, for example, electronic components (including silicon wafers, PCBs, and semiconductor surfaces), precision components (including aircraft components and components), diesel fuel, medium oil, fluorinated lubricants, greases, and silicones and waxes.

[0194] A preferred solvent vapor phase degreasing and flux removal method of the present invention involves immersing a soiled substrate or component (e.g., a printed circuit board or a processed metal, glass, ceramic, plastic, or elastomer component or composite material) or a portion of the substrate or component in a boiling non-flammable liquid according to the present invention containing the composition of the present invention, which includes composition 1; and subsequently rinsing the component in a second tank or washing zone by immersion or distillate spray with a clean solvent which may be any one of the compositions of the present invention. The component is then dried by maintaining the cooled component in condensed vapor until the temperature reaches equilibrium.

[0195] Solvent cleaning of various types of parts generally occurs in batch, hoist-assisted batch, conveyor batch, or in-line type conveyor degreasing and flux removal equipment. Parts can also be cleaned in open-top flux removal or degreasing equipment. In both types of equipment, the inlet and / or outlet ends of the equipment can be in open communication with both the ambient environment and the solvent within the equipment. To minimize solvent loss from the equipment by either convection or diffusion, common practices in the art should be used.

[0196] The present invention includes a solvent composition comprising the composition of the present invention, comprising Composition 1, in combination with a cosolvent. The cosolvent may be selected from the group consisting of hexafluoroisopropyl ethyl ether, hexafluoroisopropyl methyl thioether, HFE-7000, HFE-7200, HFE-7100, HFE-7300, HFE-7500, HFE-7600, trans-1,2-dichloroethylene, n-pentane, cyclopentane, ethanol, perfluoro(2-methyl-3-pentanone) (Novec 1230), cis-HFO-1336mzz, trans-HFO-1336mzz, HF-1234yf, HFO-1234ze(E), HFO-1233zd(E), and HFO-1233zd(Z).

[0197] Electrolyte formulations and batteries The present invention also provides an electrolyte formulation comprising the composition of the present invention comprising Composition 1, and a battery comprising the electrolyte formulation. Generally, an electrolyte formulation comprises (a) an electrolyte, (b) an organic solvent for the electrolyte, and (c) an additive included in the formulation to provide a desired property of the electrolyte formulation and / or a battery containing the electrolyte or an improvement to a desired property. The composition of the present invention comprising Composition 1 may be included in the formulation as a solvent (or co-solvent) for the electrolyte and / or as an additive.

[0198] Accordingly, the present invention provides an electrolyte formulation comprising (b) a salt, preferably a lithium-ion salt; a solvent for the salt, wherein the solvent comprises the composition of the present invention comprising composition 1, which may or may not contain a cosolvent; and one or more additives different from the compound of the present invention. The present invention also provides an electrolyte formulation comprising (b) an electrolyte, preferably a lithium-ion electrolyte; (c) a solvent for the lithium-ion electrolyte; and an additive comprising the composition of the present invention comprising composition 1, with or without additional additives.

[0199] The present invention also provides batteries in general, particularly rechargeable lithium-ion batteries, which include an electrolyte formulation comprising the composition of the present invention, comprising Composition 1. An exemplary rechargeable lithium-ion battery is illustrated in Figure 9 of this specification, which shows the cathode and anode, as well as the electrolyte formulation of the present invention that facilitates the flow of lithium ions between the cathode and anode.

[0200] The electrolyte formulations of the present invention are intended to be useful in batteries in general, but in preferred embodiments, the electrolyte formulations include lithium-ion electrolytes useful in rechargeable batteries. Non-limiting examples of lithium salts that can constitute the electrolyte portion of the formulations include LiPF6, LiAsF6, LiClO4*LiBF4, LiBC4Og(LiBOB), LiBCO4F, (LiODFB), LiPF3(C2F5)3(LiFAP), LiBF3(C2F5)LiPF3(C,F5)3(LiFAB), LiN, (CF3SO,)LiN(C,F5SO), LiCF3SO3, LiC(CF3SO)3, LiPF4(CF3)2, LiPF3(CF3)3, LiPF3(iSO-C3C7)3, and LiPF5(iso-C3F7). The overall salt concentration may vary depending on the specific needs of the application, and in some embodiments, the electrolyte may be present in the formulation in amounts of about 0.3 M to about 2.5 M, or about 0.7 M to about 1.5 M. [Examples]

[0201] Example 1 - Synthesis of HFPOHFP from HFP and HFIP HFPOHFP was synthesized from HFP and HFIP following the procedure below.

[0202] 250 mL of DMF and 10 g of cesium carbonate were placed in a 500 mL three-necked, round-bottom jacketed flask equipped with a mechanical stirrer, dry ice condenser, gas spurger (for HFP), and temperature sensor. The condenser outlet was attached to a nitrogen T-tube. The cooling water switch was turned on before adding 125 mL of HFIP. At this point, a slight exothermic reaction was observed. The reactants were cooled to below 25°C. Next, 200 g of HFP was added over 60 minutes, using the spurger and needle valve to ensure the reaction mixture temperature did not exceed 25°C. The reaction was observed to be exothermic, turning slightly yellow towards the end of the addition. As the reaction neared completion, the exothermic reaction slowed, and the reaction temperature decreased rapidly. The reaction mixture was decanted from the flask, filtered, and then evaporated by rotation at 45°C and 60–70 Torre. The heavy components were poured into water, and the lower layer (colorless liquid) was separated to obtain 325.0 g (yield 81%, GC 83.39%). Alternatively, the reaction mixture was decanted and completely rotated and evaporated under the same conditions to obtain 323.8 g (yield 80.6%, GC 82.92%). This substance was then distilled, and together, a total of 562.8 g of the substance with a yield of over 95% was obtained by GC.

[0203] The reagents used and their properties, along with the molecular weight, boiling point, and density of the resulting HFPOHFP, are shown in Table E1A below.

[0204] [Table 5]

[0205] HFPOHFP was also tested to determine its density over a temperature range using an Ubbelohde tube, following the procedure described in ASTM D2196, and the results of this test are reported in Table E2 below.

[0206] [Table 6]

[0207] As can be seen from the data above, the compositions of the present invention, including refrigerants 1 to 8, can exhibit combinations of properties, including viscosity, dielectric constant, and boiling point, that provide unexpectedly favorable performance over the temperature range of interest for many of the preferred heat transfer methods of the present invention, including heat transfer method 1.

[0208] Example 2 - Synthesis of TFE / HFP from HFP and TFE TFE / HFP is synthesized from HFP and TFE according to the following procedure: 250 mL of DMF and 10 g of cesium carbonate are placed in a 500 mL three-necked round-bottom jacketed flask equipped with a mechanical stirrer, dry ice condenser, gas spurger (for HFP), and temperature sensor. The condenser outlet is attached to a nitrogen T-tube. The cooling water is switched on before adding 86 mL of TFE. A slight exothermic reaction is observed at this point. The reactants are cooled to below 25°C. Next, 200 g of HFP is added over 60 minutes using the spurger and needle valve, ensuring that the temperature of the reaction mixture does not exceed 25°C. The reaction is observed to be exothermic, turning slightly yellow towards the end of the addition. When the reaction is almost complete, the exothermic reaction slows down and the reaction temperature drops rapidly. The reaction mixture is decanted from the flask, filtered, and then rotated and evaporated at 45°C and 60-70 Torre. The reboiled heavy components were poured into water, and the lower layer (colorless liquid) was separated to obtain 325.0202 g (yield 801%, GC 8385.39%). Alternatively, the reaction mixture was decanted and completely rotated and evaporated under the same conditions to obtain 323.8 g (yield 80.6%, GC 82.92%). This substance was then distilled, and together, a total of 562.8 g of the substance was obtained by GC using a highly sensitive method, yielding over 95%.

[0209] Example 3A - Method and use of refrigerant 1 in the fabrication of electronic components An electronic component or part thereof that is cooled during a manufacturing process (for example, in the etching of a silicon wafer, as illustrated in Figure 11) comes into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the electronic component. Effective temperature control is provided.

[0210] Example 3B - Method and Use of Refrigerants 2-8 and RB1-RB20 in the Fabrication of Electronic Components Example 3A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the electronic components while they are being processed, except that heat is transferred to and from the electronic components as part of the manufacturing process. Effective temperature control is provided.

[0211] Example 4A - Method and use of refrigerant 1 in the fabrication of semiconductor integrated circuits (ICs) A semiconductor integrated circuit and / or a part thereof, which is cooled while being processed during manufacturing, comes into direct or indirect contact with a coolant 1 as part of the manufacturing process, transferring heat to and from the semiconductor integrated circuit (to and / or from the semiconductor integrated circuit and / or a part thereof). Effective temperature control is provided.

[0212] Example 4B - Method and Use of Refrigerants 2-8 and RB1-RB20 in the Fabrication of Semiconductor Integrated Circuits (ICs) The embodiment 4A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool a semiconductor integrated circuit while it is being processed, except that heat is transferred to and from the semiconductor integrated circuit as part of the manufacturing process. Effective temperature control is provided.

[0213] Example 5A - Method and use of refrigerant 1 in the fabrication of an electrochemical cell An electrochemical cell and / or part thereof, which is cooled while being processed during manufacturing, comes into direct or indirect contact with a coolant 1 as part of the manufacturing process, transferring heat to and from the electrochemical cell (to and / or from the electrochemical cell and / or part thereof). Effective temperature control is provided.

[0214] Example 5B - Method and use of refrigerants 2-8 and RB1-RB20 in the fabrication of an electrochemical cell Example 5A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool an electrochemical cell while it is being processed, except that heat is transferred to and from the electrochemical cell as part of the manufacturing process. Effective temperature control is provided.

[0215] Example 6A - Method and use of refrigerant 1 in the fabrication of a power transistor Power transistors and / or parts thereof, which are cooled while being processed during manufacturing, come into direct or indirect contact with a coolant 1 as part of the manufacturing process, transferring heat to and from an electrochemical cell (to and / or from the electrochemical cell). Effective temperature control is provided.

[0216] Example 6B - Method and use of refrigerants 2-8 and RB1-RB20 in the fabrication of an electrochemical cell Example 6A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the power transistors while they are being processed, except that heat is transferred to and from the power transistors as part of the manufacturing process. Effective temperature control is provided.

[0217] Example 7A - Method and use of refrigerant 1 in the fabrication of an electroluminescent element An electroluminescent element and / or a part thereof, which is cooled while being processed during manufacturing, comes into direct or indirect contact with a coolant 1 as part of the manufacturing process, transferring heat to and from the electroluminescent element (to and / or from the electroluminescent element and / or a part thereof). Effective temperature control is provided.

[0218] Example 7B - Method and use of refrigerants 2-8 and RB1-RB20 in the fabrication of an electroluminescent element Example 7A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the electroluminescent element while it is being processed, except that heat is transferred to and from the electroluminescent element as part of the manufacturing process. Effective temperature control is provided.

[0219] Example 8A - Method and use of refrigerant 1 in the fabrication of a microprocessor A microprocessor and / or a part thereof, which is cooled while being processed during manufacturing, comes into direct or indirect contact with a coolant 1 as part of the manufacturing process, transferring heat to and from the microprocessor and / or a part thereof. Effective temperature control is provided.

[0220] Example 8B - Method and Use of Refrigerants 2-8 and RB1-RB20 in the Fabrication of a Microprocessor The example 8A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool a microprocessor while it is being processed, except that heat is transferred to and from the microprocessor as part of the manufacturing process. Effective temperature control is provided.

[0221] Example 9A - Method and use of refrigerant 1 in semiconductor wafer fabrication A semiconductor wafer and / or a part thereof, which is cooled during a manufacturing process (for example, in the etching of a silicon wafer as illustrated in Figure 11), comes into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the semiconductor wafer (to and / or from the semiconductor wafer and / or a part thereof). Effective temperature control is provided.

[0222] Example 9B - Method and Use of Refrigerants 2-8 and RB1-RB20 in Semiconductor Wafer Fabrication The embodiment 9A is repeated using each of the refrigerants 2 to 8 and each of the RB1 to RB2 to cool the semiconductor wafer while it is being processed, except that heat is transferred to and from the semiconductor wafer as part of the manufacturing process. Effective temperature control is provided.

[0223] Example 10A - Method and use of refrigerant 1 in the fabrication of a power control semiconductor During manufacturing, the power control semiconductor and / or a portion thereof, which are cooled while being processed, come into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the power control semiconductor (to and / or from the power control semiconductor and / or a portion thereof). Effective temperature control is provided.

[0224] Example 10B - Method and Use of Refrigerants 2-8 and RB1-RB20 in the Fabrication of Power Control Semiconductors Embodiment 10A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool a power control semiconductor while it is being processed, except that heat is transferred to and from the power control semiconductor as part of the manufacturing process. Effective temperature control is provided.

[0225] Example 11A - Method and use of refrigerant 1 in the manufacture of a power distribution switchgear During manufacturing, the power distribution switchgear and / or parts thereof, which are cooled while being processed, come into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the power distribution switchgear (to and / or parts thereof). Effective temperature control is provided.

[0226] Example 11B - Method and Use of Refrigerants 2-8 and RB1-RB20 in the Fabrication of Power Control Semiconductors Embodiment 11A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the power distribution switchgear while it is being processed, except that heat is transferred to and from the power distribution switchgear as part of the manufacturing process. Effective temperature control is provided.

[0227] Example 12A - Method and use of refrigerant 1 in the manufacture of a power transformer A power transformer and / or a part thereof, which is cooled while being processed during manufacturing, comes into direct or indirect contact with a coolant 1 as part of the manufacturing process, transferring heat to and from the power transformer (to and / or from the power transformer and / or a part thereof). Effective temperature control is provided.

[0228] Example 12B - Method and Use of Refrigerants 2-8 and RB1-RB20 in the Fabrication of a Power Transformer Each of refrigerants 2 to 8 and each of RB1 to RB2 repeats the example 12A for cooling a power transformer while undergoing processing, except that they transfer heat to and from the power distribution switchgear as part of the manufacturing process. Effective temperature control is provided.

[0229] Example 13A - Method and use of refrigerant 1 in the manufacture of printed circuit boards (PCBs) A printed circuit board (PCB) and / or a part thereof, which is cooled while being processed during manufacturing, comes into direct or indirect contact with a coolant 1 as part of the manufacturing process, transferring heat to and from the printed circuit board (PCB) and / or a part thereof. Effective temperature control is provided.

[0230] Example 13B - Method and Use of Refrigerants 2-8 and RB1-RB20 in Printed Circuit Board (PCB) Fabrication Example 13A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool a printed circuit board (PCB) while it is being processed, except that heat is transferred to and from the printed circuit board (PCB) as part of the manufacturing process. Effective temperature control is provided.

[0231] Example 14A - Method and use of refrigerant 1 in the fabrication of a multi-chip module (MCM). The MCM and / or a portion thereof, which are cooled while being processed during manufacturing, come into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the MCM (to and / or from the MCM and / or a portion thereof). Effective temperature control is provided.

[0232] Example 14B: Method and Use of Refrigerants 2-8 and RB1-RB20 in the Fabrication of MCM Example 14A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the MCM while it is being processed, except that heat is transferred to and from the MCM as part of the manufacturing process. Effective temperature control is provided.

[0233] Example 15A - Method and use of refrigerant 1 in the fabrication of packaged semiconductor devices (PSCDs) During the manufacturing process, the PSCD and / or a portion thereof, which are cooled while being processed, come into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the PSCD (to and / or from the PSCD and / or a portion thereof). Effective temperature control is provided.

[0234] Method and use of refrigerants 2-8 and RB1-RB20 in the preparation of Example 15B-PSCD Example 15A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the PSCD while it is being processed, except that heat is transferred to and from the PSCD as part of the manufacturing process. Effective temperature control is provided.

[0235] Example 16A - Method and use of refrigerant 1 in the fabrication of unpackaged semiconductor devices (USCDs). The USCD and / or a portion thereof, which are cooled while being processed during manufacturing, come into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the USCD (to and / or from the USCD and / or a portion thereof). Effective temperature control is provided.

[0236] Method and use of refrigerants 2-8 and RB1-RB20 in the fabrication of Example 16B-USCD Example 16A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the USCD while it is being processed, except that heat is transferred between the USCDs (to and / or from the USCDs) as part of the manufacturing process. Effective temperature control is provided.

[0237] Example 18A - Method and use of refrigerant 1 in the fabrication of a fuel cell During manufacturing, the fuel cell and / or a part thereof, which is cooled while being processed, comes into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the fuel cell (to and / or from the fuel cell and / or a part thereof). Effective temperature control is provided.

[0238] Example 18B - Method and Use of Refrigerants 2-8 and RB1-RB20 in the Fabrication of a Fuel Cell Example 18A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool a fuel cell while it is being processed, except that heat is transferred to and from the fuel cell as part of the manufacturing process. Effective temperature control is provided.

[0239] Example 19A - Method and use of refrigerant 1 in laser fabrication During manufacturing, the laser and / or a part thereof, which is cooled while being processed, comes into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the laser (to and / or from the laser and / or a part thereof). Effective temperature control is provided.

[0240] Example 19B - Method and use of refrigerants 2-8 and RB1-RB20 in laser fabrication Example 19A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the laser cell while it is being processed, except that heat is transferred to and from the laser as part of the manufacturing process. Effective temperature control is provided.

[0241] Example 20A - Method and use of refrigerant 1 in the fabrication of light-emitting diodes (LEDs) During manufacturing, the LEDs and / or parts thereof, which are cooled while being processed, come into direct or indirect contact with the coolant 1 as part of the manufacturing process, transferring heat to and from the LEDs (to and / or parts thereof). Effective temperature control is provided.

[0242] Example 20B - Method and use of refrigerants 2-8 and RB1-RB20 in the fabrication of LEDs Example 20A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the LEDs while they are being processed, except that heat is transferred to and from the LEDs as part of the manufacturing process. Effective temperature control is provided.

[0243] Example 21A - Method and use of refrigerant 1 in the fabrication of an electrochemical cell (EC). The EC and / or a portion thereof, which are cooled while being processed during manufacturing, come into direct or indirect contact with the refrigerant 1 as part of the manufacturing process, transferring heat to and from the EC (to and / or a portion thereof). Effective temperature control is provided.

[0244] Method and use of refrigerants 2-8 and RB1-RB20 in the preparation of Example 21B-EC Example 21A is repeated using each of refrigerants 2 to 8 and each of RB1 to RB2 to cool the EC while it is being processed, except that heat is transferred to and from the EC as part of the manufacturing process. Effective temperature control is provided.

[0245] It should be understood that the foregoing description is merely illustrative of the present disclosure. Various alternative and modified forms can be devised by those skilled in the art without departing from the present disclosure. Accordingly, the present disclosure is intended to encompass all such alternative forms, modifications, and variations that fall within the scope of the appended claims.

Claims

1. A method for manufacturing an electronic device or component, a. In the manufacturing process, to provide at least a part of an electronic device and / or a component of an electronic device, b. To provide a refrigerant containing 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane (HFPOOHFP), c. A method comprising transferring heat directly and / or indirectly between the electronic device and the components of the electronic device while the device or components are being manufactured.

2. The method according to claim 1, wherein the refrigerant is non-flammable.

3. The method according to claim 1, wherein the refrigerant comprises at least about 10% by weight of the 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane.

4. The method according to claim 1, wherein the refrigerant comprises at least about 50% by weight of the 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane.

5. The method according to claim 1, wherein the refrigerant comprises at least about 75% by weight of the 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane.

6. The method according to claim 1, wherein the refrigerant comprises at least about 90% by weight of the 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane.

7. The method according to claim 1, wherein the refrigerant essentially consists of 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane.

8. The method according to claim 1, wherein the refrigerant is 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane.

9. The method according to claim 1, wherein the refrigerant has a dielectric constant of less than about 6 at 20 GHz and a GWP of less than 500.

10. The method according to claim 1, wherein the refrigerant has a boiling point of about 60°C to about 100°C.

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