Compositions comprising fluorine substituted ether and methods and uses comprising same

Abstract

Methods of heating and / or cooling electronic components, articles and devices during operation of the electronic components, articles and devices and / or during manufacture of the electronic components, articles and devices 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

[0001] Cross - reference

[0002] This application is related to and claims the priority benefit of U.S. Provisional Application No. 63 / 415,679, filed on October 13, 2022, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] The present disclosure relates to fluorinated ethers and their use in various applications, including as heat transfer fluids for use in conjunction with the manufacture of semiconductor devices. Background Art

[0004] There remains a need for inert fluorinated fluids that have a low global warming potential while providing high thermal stability, low toxicity, non - flammability, good solubility, and a wide operating temperature range to meet the requirements of various applications.

[0005] The Applicant has recognized that many challenging problems are associated with the development of new compounds and compositions for many important applications. Specifically, the Applicant has recognized the need for compositions, methods, and systems that are simultaneously environmentally acceptable (low GWP and low ODP), non - flammable, have low toxicity or no toxicity, and have one or more properties required for a particular application. For example, refrigerants should provide appropriate heat transfer properties at the use temperatures of a particular heat transfer application, and if the heat transfer application involves exposure or potential exposure of the refrigerant to electronic equipment or components, they should also have an appropriately low dielectric constant. An example of such a use for which there is a continuing need for improved refrigerants is heat transfer required to manage / control the temperature of electronic components, devices, and articles during steps used in the manufacture and production of such electronic components, devices, and articles. This is a significant technical challenge because refrigerants often need to function effectively within a relatively wide range of processing conditions (including processing temperatures) and during the process of potential exposure to electronic devices.

[0006] Examples of electronic manufacturing processes that experience thermal management challenges include the etching of semiconductor integrated circuits, rapid thermal annealing (RTA), etc., especially as the line widths of such circuits continue to decrease. These manufacturing challenges include an 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 5,904,572 (relating to wet etching processes), U.S. 2005 / 0155555 (relating to chemical vapor deposition in semiconductor manufacturing), and U.S. 2007 / 0117362 (relating to RTA), all of which are incorporated herein by reference. These challenges are made more severe because in some electronic device cooling applications, the viscosity of the refrigerant fluid used to manage the temperature of electronic components is also required to be low enough within the operating temperature range of the refrigerant fluid so that the fluid can circulate and maintain its desired heat transfer properties.

[0007] Vapor phase soldering is another example of an electronic device manufacturing process that uses a refrigerant to help manage the processing temperature. High temperatures are used in this application, so the heat transfer fluid must be suitable for high temperature exposure (e.g., up to 250 °C). Currently, perfluoropolyethers (PFPEs, i.e., compounds having only carbon, oxygen, and fluorine) are commonly used as the heat transfer fluid in this application. Although many PFPEs have sufficient thermal stability for these high temperatures, they are environmentally persistent and have extremely long atmospheric lifetimes, which in turn results in extremely high global warming potentials (GWPs).

[0008] Improved refrigerants are also needed in the manufacture and / or operation of small electronic devices. There has been a constant desire to miniaturize electronic components while increasing functionality, which increases the thermal power density during device operation, making cooling of the electronic components within such devices more challenging. As a general rule, an increase in computing power within desktop computers, data centers, telecommunication centers, etc. results in an increase in the heat output during operation of such devices, which also makes thermal management of electronic devices during manufacture and / or operation increasingly important, difficult, and demanding.

[0009] Another example of a challenge in providing refrigerants for thermal management is the increasing use of electric vehicles, including in particular cars, trucks, motorcycles, etc. In electric vehicles, the thermal management function is particularly important and challenging for several reasons, including the criticality of cooling and / or heating the battery to a relatively narrow temperature range in a reliable, efficient, and safe manner, and as the demand for battery-powered vehicles with greater range and faster charging increases, the challenge of providing effective thermal battery management becomes increasingly greater.

[0010] The efficiency and effectiveness of batteries, especially those that provide power in electric vehicles, are a function of the operating temperature at which they operate. Therefore, a thermal management system must often be able to do more than just remove heat from the battery during operation and / or charging, but must also be able to achieve cooling within a relatively narrow temperature range using equipment that is as low cost and as light weight as possible. This results in a need for refrigerants in such systems with a combination of physical and performance characteristics that are difficult to achieve. In addition, in some important applications, the thermal management system must be able to add heat to the battery, especially when the vehicle is starting in cold weather, not only from the perspective of thermal performance, but also from many other perspectives including environmental, safety (flammability and toxicity), dielectric properties, etc., which further increases the difficulty of finding and developing / obtaining compounds and / or compositions that are effective in such systems.

[0011] As a specific example of the importance of the dielectric constant, a system commonly used for the thermal management of electric vehicle batteries involves immersing the batteries in a fluid used for thermal management. Such systems add an additional constraint, namely, that when the battery or device is operating, the fluid used in such systems must be electronically compatible by virtue of being in close contact with the battery or other electronic devices or components. Generally speaking, this means that the fluid must not only be non-flammable, but also have low electrical conductivity and a high level of stability when in contact with the battery or other electronic components during operation and at the relatively high temperatures present during operation. The applicant has recognized that such properties are also required even in the indirect cooling of operating electronic devices and batteries, since any leakage of such a fluid could result in contact with operating electronic components.

[0012] Water / glycol combinations are commonly used for battery cooling, including immersion cooling, and other classes of materials have been mentioned, including some chlorofluorocarbons, fluorocarbons, chlorocarbons, and hydrofluoroethers are also usable. See, for example, US2018 / 0191038.

[0013] US2023 / 0200010 discloses the use of certain fluorinated ethers for cooling electronic equipment, specifically by at least partially immersing the electronic equipment in a fluorine-based fluid that is alleged to have a boiling point of 50 °C to 60 °C.

[0014] JP 2005 / 047856 discloses the use of several fluorinated ether compounds as refrigerants, cleaning agents, etc.

[0015] Fluorinated ether compounds according to the following formula have been proposed for use as solvents, particularly for various fluorinated polyethers,

[0016] (F 3 C) 2 CH-O-CH n F 2-n -CH m F 3-m

[0017] where n is 1 or 2, and where when n is 1, m is any integer from 0 to 3, but when n is 2, then m is 0 or 2. See JP202105950. This document states that embodiments of the above formula that are alleged to have a 3-1 configuration (should be understood to mean m = 3 and n = 1) have additional uses, including as drainage agents, foaming agents, heat transfer media, and fire extinguishing agents, but do not specifically describe or give examples of such uses.

[0018] Accordingly, the Applicant has recognized that in addition to other needs described herein, there is a need for such thermal management methods and systems that use refrigerants that are environmentally acceptable (relatively low GWP and low ODP), non-flammable, have low toxicity or no toxicity, and have excellent thermal properties for providing effective cooling and / or heating, especially in electronic devices and semiconductor manufacturing processes involving relatively high temperatures and / or for maintaining process conditions within a relatively narrow temperature range. For example, the Applicant has found that fluids having a relatively low boiling point (e.g., below about 60 °C) are undesirable in many applications involving the manufacture of electronic components, as further explained below. Summary of the Invention

[0019] 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"). The composition according to this paragraph is sometimes referred to herein as Composition 1A for convenience.

[0020] The present invention includes a composition comprising 1,1,1,2,3,3,-hexafluoro-3-(2,2,2-trifluoroethoxy)propane or a combination of the foregoing. The composition according to this paragraph is sometimes referred to herein as Composition 1B for convenience.

[0021] The present invention includes a composition 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 composition according to this paragraph is sometimes referred to herein as Composition 1C for convenience.

[0022] The present invention includes a refrigerant comprising HFPOHFP. The refrigerant according to this paragraph is sometimes referred to herein as Refrigerant 1 for convenience.

[0023] The present invention includes a refrigerant comprising at least about 10 wt% HFPOHFP. The refrigerant according to this paragraph is sometimes referred to herein as Refrigerant 2 for convenience.

[0024] The present invention includes a refrigerant comprising at least about 50 wt% HFPOHFP. The refrigerant according to this paragraph is sometimes referred to herein as Refrigerant 3 for convenience.

[0025] The present invention includes a refrigerant comprising at least about 75 wt% HFPOHFP. The refrigerant according to this paragraph is sometimes referred to herein as Refrigerant 4 for convenience.

[0026] The present invention includes a refrigerant comprising at least about 90 wt% HFPOHFP. The refrigerant according to this paragraph is sometimes referred to herein as Refrigerant 5 for convenience.

[0027] The present invention includes a refrigerant consisting essentially of HFPOHFP. The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 6 for convenience.

[0028] The present invention includes a refrigerant consisting of HFPOHFP. The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 7 for convenience.

[0029] The present invention includes a refrigerant containing 1,1,1,2,3,3 - hexafluoro - 3 - (2,2,2 - trifluoroethoxy) propane (sometimes referred to hereinafter as "TFE / HFP"). The refrigerant according to this paragraph is sometimes referred to herein as refrigerant 8 for convenience.

[0030] The present invention includes a method for synthesizing a fluoroether from a fluoroolefin and a fluoroalcohol, the method comprising reacting the fluoroalcohol with the fluoroolefin in the presence of a catalyst to provide the fluoroether. The method according to this paragraph is sometimes referred to herein as synthesis method 1 for convenience.

[0031] The present invention includes a method for cooling and / or heating an electronic device in operation and / or cooling and / or heating an electronic component, device or article during its manufacture, the method comprising: providing a refrigerant containing HFPOHFP, including 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, preferably including immersing at least a portion of the electronic component, device or article in the refrigerant. The method according to this paragraph is sometimes referred to herein as heat transfer method 1A for convenience.

[0032] The present invention includes a method for cooling and / or heating an electronic component, device or article during its manufacture, the method comprising: providing a refrigerant containing HFPOHFP, including each of refrigerants 1 to 7; and thermally connecting the electronic component, device or article to the refrigerant during the process of manufacturing the electronic component, device or article to heat and / or cool the electronic component, device or article. The method according to this paragraph is sometimes referred to herein as heat transfer method 1B for convenience. Description of the Drawings

[0033] The above and other features of the present disclosure and the manner of achieving them will become more apparent and the present disclosure itself will be better understood by reference to the following description of embodiments of the present disclosure in conjunction with the accompanying drawings.

[0034] Figure 1 It is a schematic diagram of the thermal management system of the present invention.

[0035] Figure 2ASchematic diagram of a first exemplary immersion cooling system according to the present invention.

[0036] Figure 2B Schematic diagram of a second exemplary immersion cooling system according to the present invention.

[0037] Figure 3 is a schematic diagram of a battery thermal management system according to an embodiment of the present invention.

[0038] Figure 4 Photo showing a battery thermal management system according to an embodiment of the present invention.

[0039] Figure 5 Schematic diagram of an exemplary organic Rankine cycle.

[0040] Figure 6 Schematic diagram of an exemplary heat pump.

[0041] Figure 7 Schematic diagram of an exemplary secondary loop system.

[0042] Figure 8 Semi-schematic diagram of an example of a lithium-ion battery cooling system using the composition of the present invention.

[0043] Figure 9 Semi-schematic diagram of an example of a lithium-ion battery having the electrolyte formulation of the present invention.

[0044] Figure 10 Semi-schematic diagram of a heat dissipation tube using the heat transfer composition of the present invention.

[0045] Figure 11 Side cross-sectional view of a conventional wet etching station. Detailed Description

[0046] I. Definitions

[0047] The terms "R-1132(E)", "HFO-1132(E)" and "trans-HFO-1132(E)" each refer to the trans isomer of 1,2-difluoroethylene.

[0048] The terms "R-1132a" and "HFO-1132a" each refer to 1,1-difluoroethylene.

[0049] The terms "R-1234yf" and "HFO-1234yf" refer to 2,3,3,3-tetrafluoropropene.

[0050] The terms "R-1234ze(E)" and "HFO-1234ze(E)" refer to the trans isomer of 1,3,3,3-tetrafluoropropene.

[0051] The terms "R-1233zd(E)" and "HFCO-1233zd(E)" refer to the trans isomer of 1-chloro-3,3,3-trifluoropropene.

[0052] The terms "R-1233zd(Z)" and "HFCO-1233zd(Z)" refer to the cis isomer of 1-chloro-3,3,3-trifluoropropene.

[0053] The terms "R-1224yd(E)" and "HFCO-1224yd(E)" refer to the trans isomer of 1-chloro-2,3,3,3-tetrafluoropropane.

[0054] The terms "R-1224yd(Z)" and "HFCO-1224yd(Z)" refer to the cis isomer of 1-chloro-2,3,3,3-tetrafluoropropane.

[0055] The terms "R-1336mzz(E)" and "HFO-1336mzz(E)" refer to the trans isomer of 1,1,1,4,4,4-hexafluoro-2-butene.

[0056] The term "HFE-7000" refers to 1-methoxyheptafluoropropane (C 3 F 7 OCH 3 ).

[0057] The term "HFE-7100" refers to 1-methoxynonafluorobutane (C 4 F 9 OCH 3 ).

[0058] The term "HFE-7200" refers to ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 ).

[0059] The term "HFE-7300" refers to 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethylpentane.

[0060] The term "HFE-7500" refers to 2-trifluoromethyl 3-ethoxydodecafluorohexane.

[0061] As used herein, reference to a defined group (such as "RB1 to RB2") (see Table 4 below) refers to each refrigerant blend within the group, including those in which the defined numbers include a suffix. Thus, reference to "RB1 to RB2" includes reference to each of RB1A, RB1B, etc. and RB2A, RB2B, etc.

[0062] The names of the compounds used herein, along with their corresponding chemical names and chemical formulas, are provided in Table 1 below.

[0063] Table 1

[0064]

[0065] "Electronic device" and related forms refer to a device or a 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. Thus, as used herein, the term "electronic device in operation" includes, for example, a battery that is in the process of being a source of electrical energy for another component, and also includes, for example, a battery that is being charged or recharged.

[0066] The term "refrigerant" and related forms refer to a fluid (liquid or gas) used to transfer heat or energy to (for heating) and / or from (for cooling) a fluid, article, or device.

[0067] "Electronic device in operation" and related forms refer to a device or a 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. Thus, as used herein, the term "electronic device in operation" includes, for example, a battery that is in the process of being a source of electrical energy for another component, and also includes, for example, a battery that is being charged or recharged.

[0068] "Thermal contact" and related forms include direct contact with a surface and indirect contact through another body or fluid that facilitates heat flow between the surface and the fluid.

[0069] "Thermal conductivity" refers to the breakdown voltage in kV as measured according to ASTM D7896-19.

[0070] The "Global Warming Potential ("GWP")" was established to allow comparison of the global warming impacts of different gases. It is a measure of how much energy one ton of a gas emitted will absorb over a given time period relative to one ton of carbon dioxide emitted. The greater the GWP, the warmer the gas will make the Earth compared to CO2 over that time period. The time period commonly used for GWP is 100 years. GWP provides a common measure - allowing analysts to accumulate emissions estimates for different gases.

[0071] "LC50" is a measure of the acute toxicity of a compound. The acute inhalation toxicity of a compound can be evaluated using the methods described in the following guidelines: OECD Chemicals Testing Guideline No. 403, "Acute Inhalation Toxicity" (2009), Method B.2. (Inhalation), Commission Regulation (EC) No. 440 / 2008.

[0072] The term "Ames negative" means a compound or composition that returns a negative result when tested in the Ames test as defined in the Toxic Substances Control Act in the United States.

[0073] "Flash point" means the lowest temperature at which the vapor of a liquid will continue to burn after removal of an ignition source, as determined in accordance with ASTM D3828-16a.

[0074] "Non-flammable" in the context of a heat transfer composition, including a thermal management composition or fluid, means a compound or composition that does not have a flash point below 100°F (37.8°C) in accordance with NFPA 30: Flammable and Combustible Liquids Code. The flash point of a thermal management composition or fluid means the lowest temperature at which the vapor of the composition will continue to burn after removal of an ignition source, as determined in accordance with ASTM D3828-16a.

[0075] In the context of a refrigerant composition, a compound or composition that is non-flammable and of low toxicity or non-toxic will be classified as "A1" in accordance with ASHRAE Standard 34-2016 "Designation and Safety Classification of Refrigerants" and described in Appendix B1 of ASHRAE Standard 34-2016.

[0076] "Non-toxic" or "low toxicity" means a fluid that is classified as Class "A" by ASHRAE Standard 34-2016 "Designation and Safety Classification of Refrigerants" and described in Appendix B1 of ASHRAE Standard 34-2016.

[0077] "Capacity" is the amount of cooling provided by the refrigerant in a refrigeration system (in BTU / hr). This is determined experimentally by multiplying the change in enthalpy (in BTU / lb) of the refrigerant as it passes through the evaporator by the mass flow rate of the refrigerant. The enthalpy can be determined from measurements of the pressure and temperature of the refrigerant. The capacity of a refrigeration system relates to the ability to keep an area cooled at a specific temperature. The capacity of a refrigerant represents the amount of cooling or heating it provides and gives some measure of the ability of the compressor to pump heat for a given volumetric flow rate of refrigerant. In other words, for a given compressor, a refrigerant with a higher capacity will deliver more cooling or heating power.

[0078] The "Coefficient of Performance" (hereinafter referred to as "COP") is a generally accepted measure of refrigerant performance and is particularly useful for expressing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving refrigerant evaporation or condensation. In refrigeration engineering, this term represents the ratio of the useful refrigeration or cooling capacity to the energy exerted by the compressor in compressing the vapor and thus represents the ability of a given compressor to pump heat for a given volumetric flow rate of a heat transfer fluid such as a refrigerant. In other words, for a given specific compressor, a refrigerant with a higher COP will deliver more cooling or heating power. One method for estimating the COP of a refrigerant under specific operating conditions is to estimate from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, for example, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, which is incorporated herein by reference in its entirety).

[0079] "Vapor degreasing" refers to a surface cleaning process that uses solvent vapor to wash oil and other contaminants off an article or a part of an article.

[0080] "Dielectric constant" refers to the dielectric constant as measured according to ASTM D150-11 at room temperature and 20 gigahertz (GHz) (unless some other test method, temperature, and gigahertz are specifically mentioned).

[0081] "Dielectric strength" refers to the breakdown voltage in kV as measured according to ASTM D87-13, Procedure A, with the modification that the spacing between the electrodes is 2.54 mm and the rate of rise is 500 V / sec.

[0082] As used herein, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise.

[0083] As used herein, the recitation of a numerical range by endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0084] Unless otherwise indicated, all numbers expressing quantities or ingredients, properties measurements, and so forth used in the specification and the examples are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached examples list may vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings of the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claimed embodiments, each numerical parameter should at least be construed in accordance with the number of reported significant digits and by applying ordinary rounding techniques.

[0085] As used herein, the phrase "in any range that encompasses any two of the foregoing values as endpoints" literally means that any range may be selected from any two of the values listed prior to such phrase, regardless of whether those values are in the lower portion or the higher portion of the list. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.

[0086] II. Synthesis from Fluoroolefins and Fluoroalcohols

[0087] 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.

[0088] Scheme 1

[0089] Scheme Amendment for the Synthesis of HFPOHFP from HFIP and HFP

[0090]

[0091] 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.

[0092] Scheme 2

[0093] Synthesis of TFE / HFP from TFE and HFP

[0094]

[0095] The refrigerant of the present invention and / or the TFE / HFP compound used in the systems and methods according to the present invention has a boiling point of about 72 °C, a density of about 1.54, and a dielectric constant (less than 5.4 at 20 GHz).

[0096] In a preferred embodiment, the starting materials HFP and TFE or HFIP can be present in a stoichiometric ratio of 0.8:1.2 to 1.2:0.8. For example, HFP and TFE can have a stoichiometric ratio of 0.9:1.1, 1.1:0.9, or 1:1.

[0097] The reaction can preferably be carried out in an organic solvent such as dimethylformamide (DMF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF), etc.

[0098] The reaction can preferably be catalyzed by a base such as cesium carbonate (Cs 2 CO 3 ) or other suitable organic or inorganic bases.

[0099] The reaction can preferably be carried out in a reactor using a sufficient level of agitation to produce a homogeneous reaction mixture. Suitable agitation can be achieved by using a mechanical stirrer or a magnetic stir bar. The reactor vessel can be connected to a heating medium to maintain an appropriate reaction temperature. The reactor vessel can be connected to a cooling bath with any suitable cooling medium to maintain an appropriate reaction temperature. The reactor vessel can also be connected to a condenser with a cooling medium to condense the solvent vapor.

[0100] The reaction can preferably be carried out at a temperature as low as 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C or as high as 30 °C, 35 °C, 40 °C, 45 °C, 50 °C or within any range covered by any two of the foregoing values as endpoints. For example, the reaction can be carried out at a temperature of 10 °C to 25 °C.

[0101] III. Applications of HFPOHFP and TFE / HFP Fluoroethers

[0102] A summary of the physical properties of the refrigerant of the present invention and / or HFPOHFP used in the systems and methods according to the present invention is provided in Table 2 below.

[0103] Table 2

[0104]

[0105] These compositions (including each of Compositions 1A to 1C) can be used in a variety of applications, including but not limited to: (1) refrigerants for a variety of heat transfer applications (including thermal management systems and methods); (2) aerosol propellants; (3) blowing agents; (4) gaseous dielectrics; (5) fire extinguishing agents; (6) solvents; (7) cleaners; (8) working fluids for power cycles; (9) electrolytes; and (10) starting materials for the production of other organofluorine compounds.

[0106] The preferred refrigerants of the present invention (including each of refrigerants 1 to 8) are particularly and unexpectedly advantageous in heat transfer applications and methods (especially including applications and methods related to the manufacture of electronic components (preferably including semiconductor manufacture)). These advantages partly stem from the preferred compositions, especially including each of refrigerants 1 to 7, because the refrigerants of the present invention have a favorable combination of properties, including viscosity and / or non-flammability. In specific applications where electronic components are exposed to or may be exposed to the refrigerant, such as during the manufacture of electronic components, a low dielectric constant is also an important property of the refrigerant.

[0107] The present invention includes the refrigerants of the present invention, including refrigerant 1 to refrigerant 7, wherein the refrigerant is non-flammable.

[0108] The present invention includes the refrigerants of the present invention, including refrigerant 1 to refrigerant 7, wherein the refrigerant has a dielectric constant of less than 3 at 20 GHz.

[0109] The present invention includes the refrigerants of the present invention, including refrigerant 1 to refrigerant 7, wherein the refrigerant has a dielectric constant of 2.5 or less at a frequency of 20 GHz or lower.

[0110] The present invention includes the refrigerants of the present invention, including refrigerant 1 to refrigerant 7, wherein the refrigerant has a dielectric constant of less than 5 at 20 GHz; (ii) has a boiling point of about 35 °C to about 80 °C; (iii) is non-flammable; and (iv) has Ames negative toxicity.

[0111] The present invention includes the refrigerants of the present invention, including refrigerant 1 to refrigerant 7, wherein the refrigerant has a boiling point of about 35 °C to about 80 °C.

[0112] Specific reference Figure 11 , shows a side cross-sectional view of a basic refrigerant-cooled wet etching station. The basic operation of such a wet etching station includes providing a container 15 that houses a bath of chemical etchant 13 for etching a plurality of semiconductor wafers 11. The temperature of the chemical etchant 13 is preferably maintained as uniform as possible, with the aim of maintaining the surfaces of the wafers 11 such that they are uniformly etched by immersion in the bath of chemical etchant 13 in the container 15. To help maintain this uniform temperature, a plurality of cooling lines 17 are installed in a part of the container 15 that houses the chemical etchant bath 13, such that the cooling lines 17 are in contact with the chemical etchant 13. During the wet etching process, the refrigerants of the present invention (especially including each of refrigerants 1 to 8) circulate through the coolant lines 17 and transfer heat from the chemical etchant through sensible temperature changes or phase changes and / or a combination of sensible temperature changes and phase changes.

[0113] As described above, the present invention includes methods and uses related to process cooling in the manufacture of electronic components (specifically including integrated circuit formation (including etching, deposition, etc.) and microchip formation (including etching, deposition, etc.)) or as part of such processes using the refrigerants of the present invention (including Refrigerant 1 to Refrigerant 7).

[0114] The following table defines some preferred uses of the refrigerants of the present invention and methods of using the refrigerants of the present invention. The first column of Table 3 below identifies and defines the uses as Use 1, Use 2, etc., and in the second column, the refrigerants identified as Refrigerant 1 to 8 above are identified and defined using the abbreviations Ref.1, Ref.2, etc. The name "NR" should be understood to mean that the component or characteristic is not necessary (but may be present) for the uses defined in each specific row of the table.

[0115] Table 3

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] In other cases, when excess heat cannot be controlled solely by air cooling, such as during a data tsunami, the refrigerants of the present invention (including each of Refrigerant 1 to Refrigerant 8) can be used in data centers. In such cases, immersion cooling of electronic components, devices, and / or articles may be required, and the refrigerants of the present invention (including each of Refrigerant 1 to Refrigerant 8) can be used in such immersion cooling systems to effectively remove heat while maintaining data transmission integrity, which is crucial in, for example, microprocessing equipment and battery cooling.

[0122] Exemplary applications of the refrigerants of the present invention are discussed below, including applications with immersion cooling.

[0123] Heat Transfer Applications

[0124] As described above, the present invention provides various methods, processes, and uses of the refrigerants of the present invention (including each of refrigerants 1 to 8) for transferring heat from one location to another (or from one body, article, or fluid to another body, article, or fluid). For example, the refrigerants of the present invention (including each of refrigerants 1 to 8) can be used to maintain the temperature of components, devices, and / or articles below a defined upper temperature and / or above a defined lower temperature, particularly including electronic components, devices, and articles. In another example, the refrigerants of the present invention (which include the refrigerants of the present invention (including each of refrigerants 1 to 8)) can be used for energy conversion, such as capturing waste heat from industrial or other processes and converting it into electrical or mechanical energy.

[0125] Thermal Management Systems and Methods

[0126] One important class of uses of the refrigerants of the present invention 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 (including each of refrigerants 1 to 8)) in a thermal management system (hereinafter sometimes referred to as a TMS) that operates to maintain an article, device (preferably an electronic component, device, article (including a battery)), or fluid within a specific temperature range, particularly when the article, device, or fluid operates 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, the TMS can maintain the temperature of the device below a defined upper temperature and / or above a defined lower temperature, including during its processing / manufacture.

[0127] The refrigerants of the present invention (including each of refrigerants 1 to 8) can be used with a variety of co-refrigerants. Preferred co-refrigerants include hexafluoroisopropyl ethyl ether, hexafluoroisopropyl methyl sulfide, HFE-7000, HFE-7200, HFE-7100, HFE-7500, trans-1,2-dichloroethylene, n-pentane, cyclopentane, ethanol, perfluoro(2-methyl-3-pentanone) (Novec 1230), cis-HFO-1336mzz, trans-HFO-1336mzz, HFO-1234yf, HFO-1234ze(E), HFO-1233zd(E), or HFO-1233zd(Z).

[0128] Table 4 below defines some preferred refrigerants, which are blends containing HFPO HFP and at least one co-refrigerant. The first column of the table numerically identifies and defines the refrigerant blends as RB1, RB2, etc., and in this column, the abbreviations COMP, CEO, and CO are used to identify the nature of the blend components identified in columns 2 and 3. Specifically, the name COMP in column 1 indicates that the refrigerant contains HFPO HFP and the indicated co-refrigerant. The name CEO in column 1 indicates that the refrigerant consists essentially of HFPO HFP and the specified co-refrigerant, and the name CO in column 1 indicates that the refrigerant consists of HFPO HFP and the specified co-refrigerant. The second column indicates the amount of HFPO HFP that needs to be present in the blend. In the third column, the co-refrigerant is identified, and if a specific amount of the co-refrigerant is required in the blend, this is also indicated.

[0129] Table 4

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] The present invention includes the refrigerant blends of the present invention, including each of RB1 to RB20, wherein the refrigerant is non-flammable.

[0136] The present invention includes the refrigerant blends of the present invention, including each of RB1 to RB20, wherein the refrigerant has a dielectric constant of less than 3 at 20 GHz.

[0137] The present invention includes the refrigerant blends of the present invention, including each of RB1 to RB20, wherein the refrigerant has a dielectric constant of less than 2.5 at 20 GHz.

[0138] The present invention includes the refrigerant blends of the present invention, including each of RB1 to RB20, wherein the refrigerant has a dielectric constant of less than 5 at 20 GHz; (ii) has a boiling point of about 35°C to about 80°C; (iii) is non-flammable; and (iv) has Ames negative toxicity.

[0139] The present invention includes the refrigerant blends of the present invention, including each of RB1 to RB20, wherein the refrigerant has a boiling point of about 35°C to about 80°C.

[0140] As discussed above, and in particular as set forth in Table 3, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can advantageously be used in a method or apparatus or system for cooling and / or heating an electronic device and / or in a method or apparatus or system for manufacturing an electronic component, device, or article (such as a semiconductor wafer or integrated circuit chip).

[0141] Now in connection with Figure 1 a preferred embodiment of the thermal management method of the present invention will be discussed. An electronic device in operation is schematically shown as 10, which has a source of electrical energy and / or signal 20 flowing into and / or out of the device 10 and generates heat due to its operation based on the electrical energy and / or signal 20. The refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) are arranged to be in thermal contact with the device 10 in operation such that heat is removed as represented by the outflow arrow 30. Heat is removed from the electronic device in operation by adding sensible heat to the liquid thermal management fluid of the present invention (i.e., increasing the temperature of the liquid), or by causing a phase change of the thermal management liquid (i.e., evaporating the liquid) or a combination of these. In a preferred embodiment, these methods provide a supply of the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) to the device 10 such that the heat flow 30 of the refrigerants of the present invention flowing from the device 10 maintains the electronic device in operation at or within a preferred operating temperature range. In a preferred embodiment, the preferred operating temperature range of the electronic device is from about 70°C to about 150°C, and even more preferably from about 70°C to about 120°C, and the heat flow 30 of the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) flowing from the device 10 maintains the electronic device in operation at or within such a preferred temperature range. Preferably, the refrigerant 30 of the present invention that has absorbed heat from the device is in thermal contact with a heat sink (schematically shown as 40) at a temperature lower than the temperature of the heat transfer fluid 30, thereby transferring the heat generated by the device 10 to the heat sink 40. Thus, the heat-depleted refrigerant 50 can return to the electronic device 10 to repeat the cooling cycle.

[0142] In a preferred embodiment of the method of the present invention, the step of removing heat by the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) includes evaporating the refrigerant using the heat generated by the operation of the electronic device, and the step of transferring the heat from the refrigerant to the radiator includes condensing the refrigerant by discharging the heat to the radiator. In such a method, the temperature of the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) during the evaporation step is preferably higher than 50 °C, or preferably higher than about 55 °C, or preferably in the range of about 55 °C to about 85 °C, or preferably about 65 °C to about 75 °C. The applicant has found that the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) provides excellent performance in such a method, while allowing the use of relatively low-cost, lightweight and reliable equipment to provide the necessary cooling, as will be further described in connection with the specific embodiments described below Figure 2A as further described.

[0143] In another preferred embodiment of the method of the present invention, the step of removing heat by the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) includes adding sensible heat to the refrigerant using the heat generated by the operation of the electronic device (for example, raising the liquid temperature to a maximum of about 70 °C or less at about atmospheric pressure, i.e., where there is no need for the fluid to be in a high-pressure container or vessel), and the step of transferring the heat from the refrigerant to the radiator to reduce the liquid temperature by discharging the heat to the radiator. The cooled liquid then returns to make thermal contact with the electronic device, where the cycle restarts. In a preferred embodiment, the temperature of the refrigerant transferring heat to the radiator is higher than about 40 °C, or preferably higher than about 55 °C, or preferably in the range of about 45 °C to about 70 °C, or preferably in the range of about 45 °C to about 65 °C, and preferably at a pressure of about atmospheric pressure. The applicant has found that the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) provides excellent performance in such a method, while allowing the use of relatively low-cost, lightweight and reliable equipment to provide the necessary cooling, as will be further described in connection with the specific embodiments described below Figure 2B as further described.

[0144] Those skilled in the art should understand that the present invention includes systems and methods that use both sensible heat transfer and phase change heat transfer as described above.

[0145] Now, in connection with Figure 2A and Figure 2BDescribes a specific method according to the present invention, wherein the electronic device 10 is housed in a suitable container 12, preferably in a sealed container, and is in direct contact with the liquid refrigerant 11A of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20), preferably completely immersed therein (schematically shown by the grey shading). For convenience, such cooling methods, devices and systems are sometimes referred to herein as "immersion cooling" methods, devices and systems.

[0146] In immersion cooling methods, devices and systems for cooling electronic devices or components, the working electronic device 10 has a source of electrical energy and / or signals 20 flowing into and / or out of the container 12 and into and / or out of the device 10, and the working electronic device generates heat due to its operation based on the electrical energy and / or signals 20. Those skilled in the art will understand that finding a refrigerant that can operate effectively in such applications is a significant challenge, because the fluid must not only provide all of the above other properties, but must also be able to do so while in close contact with a working electronic device (i.e., an electronic device involving current / signal flow). It should be understood that many fluids that may be feasible in such applications in other ways will not be available, because they will short-circuit the device, deteriorate when exposed to the conditions generated by the operation of the electronic device (i.e., reduce the cooling effect and / or the operating stability of the device over time), or have some other property that is harmful to the operation when in contact with the working electronic device.

[0147] In contrast, the thermal management method of the present invention produces excellent and unexpected results by providing the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20), which is in direct thermal contact and physical contact with the device 10 during its operation. The working heat is safely and effectively transferred to the refrigerant 11A by: (a) evaporating the liquid phase of the fluid refrigerant to form a vapor 11B; or (b) raising the temperature of the liquid refrigerant 11A; or (c) a combination of (a) and (b).

[0148] When the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) is a single-phase liquid, it will remain liquid when heated by a heat-generating component. Therefore, the refrigerant can be brought into contact with the heat-generating component to remove heat therefrom and produce a refrigerant with a higher temperature. The refrigerant is then transported to a secondary cooling circuit, such as a radiator or another refrigeration system. An example of such a system is shown in Figure 2, where the refrigerant enters and exits a battery pack housing containing a plurality of battery cells, thereby absorbing heat from the battery pack.

[0149] When the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) exists in a two-phase state, the heat-generating component is in thermal contact with the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) and transfers heat to the refrigerant, causing it to boil. Then, the refrigerant is condensed. An example of such a system is one in which the heat-generating component is immersed in the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) and an external cooling circuit condenses the boiling fluid into a liquid state.

[0150] Regarding the phase change heat transfer system of the present invention, reference is made herein Figure 2A . In this operation, as the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) evaporates and the vapor rises through the remaining refrigerant liquid in the container 12, heat is carried away from the device 10. The refrigerant vapor 11B then discharges the heat it has absorbed to the radiator 40, which can be a closed radiator 40A and / or an external radiator 40B. Examples of radiators inside the container 12 are condenser coils 30A and 30B, which have a circulating liquid with a temperature lower than the condensation temperature of the refrigerant vapor, such as water. An example of a radiator outside the container 12 will pass relatively cold ambient air over the container 12 (preferably including fins, etc. in this case), which will be used to condense the heat-transfer vapor 11B on the inner surface of the container. As a result of this condensation, the liquid refrigerant returns to the pool of the liquid fluid 11A, and the device 10 remains immersed in this pool during operation.

[0151] Regarding the sensible heat transfer system of the present invention, reference is made herein Figure 2B . In this operation, as the temperature of the liquid 11A (including the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20)) rises when receiving the heat generated by the device, heat is carried away from the device, which is immersed and preferably substantially completely immersed in the refrigerant 11A of the present invention. The higher-temperature refrigerant liquid 11A then discharges the heat it has absorbed to the radiator 40, which can be a closed radiator 40A and / or an external radiator 40B. Examples of radiators inside the container 12 are cooling coils 30A and 30B, which have a circulating liquid with a temperature lower than the temperature of the heated liquid, such as water. An example of a radiator outside the container 12 will remove the heated liquid 11A from the container through a conduit 45, in which the heated liquid is in thermal contact with a cooling fluid, such as can be provided by relatively cold ambient air, or cooling water or refrigerant, which will be used to reduce the temperature of the liquid. The cooled liquid then returns via the conduit 46.

[0152] Optionally, but preferably in certain embodiments related to the thermal management of batteries for electric vehicles, the thermal management system includes a heating element capable of heating the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20), such as, for example, an electric heating element 60 also immersed in the refrigerant. Those skilled in the art will understand that the battery in an electric vehicle (which will correspond to the Figure 2A and Figure 2B working electronic device 10 therein) can reach relatively low temperatures when parked outdoors during the winter months in many geographical locations, and in many cases such low temperature conditions are undesirable for battery operation. Accordingly, the thermal management system of the present invention may include sensors and a control module (not shown) that turn on the heating element when the battery temperature is below a predetermined level. In such a case, the heater 60 will be activated, the refrigerant liquid 11A will be heated, and in turn the heat will be transferred to the electronic device 10 until the minimum temperature is reached. Thereafter, during operation, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) will perform the cooling function as described above.

[0153] For the purposes of the present invention, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) may be in direct contact with the heat-generating component or in indirect contact with the heat-generating component.

[0154] When the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) are in indirect contact with the heat-generating component, the refrigerant fluid may be used in a closed system in an electronic device, and the closed system may include at least two heat exchangers. When using the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) to cool the heat-generating component, heat may generally be transferred from the heat-generating component to the refrigerant through a heat exchanger in contact with at least a portion of the heat-generating component, or the heat may be transferred to the circulating air, and the circulating air may conduct the heat to a heat exchanger in thermal contact with the refrigerant.

[0155] In a particularly preferred feature of the present invention, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) are in direct contact with the heat-generating component. Specifically, the heat-generating component is completely or partially immersed in the refrigerant. Preferably, the heat-generating component is completely immersed in the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20). The refrigerant, as a warm fluid or as a vapor, may then be circulated to a heat exchanger that obtains heat from the fluid or vapor through a radiator (such as ambient air or water cooled by ambient air or otherwise) and transfers the heat to the external environment. After this heat transfer, the cooled refrigerant (cooled or condensed) is recycled back into the system to cool the heat-generating component.

[0156] If the fluid comes into direct contact with the electronic components of the electronic device (such as by direct immersion cooling), or if the refrigerant leaks from the cooling circuit or spills during maintenance and comes into contact with the circuitry, the electrical conductivity and / or dielectric strength of the refrigerant become important. Accordingly, the refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) are preferably electrically insulating thermal management fluids.

[0157] The refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) can be passively or actively recycled in the device, for example by using mechanical equipment such as pumps. In a preferred feature of the present invention, the refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) are passively recycled in the device.

[0158] The passive recycling system works by transferring heat from the heat-generating component to the refrigerant until it is typically vaporized, thereby allowing the heated vapor to travel to a heat exchange surface where the heated vapor transfers its heat to the heat exchanger surface and condenses back to a liquid. It should be understood that the heat exchange surface can be part of a separate heat exchange unit and / or can be integral with the container, as described above, for example in connection with Figure 2.

[0159] The condensed liquid then preferably returns completely passively to the refrigerant in contact with the heat-generating component by gravity and / or a wicking structure. Accordingly, in a preferred feature of the present invention, the step of transferring heat from the heat-generating component to the refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) causes the thermal management fluid to evaporate.

[0160] Examples of passive recycling systems include heat pipes or thermosyphons. Such systems passively recycle the refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) using gravity. In such systems, the refrigerant is heated by the heat-generating component, thereby creating a heated refrigerant with a lower density and greater buoyancy. The refrigerant travels to a storage container, such as a tank where the refrigerant is cooled and condensed. The cooled refrigerant then flows back to the heat source.

[0161] Electrical Equipment Cooling

[0162] The present disclosure includes the use of the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) for cooling and optionally heating an electronic device that generates or includes a component as a heat-generating component. The heat-generating component can be any component that includes an electronic element that generates heat as part of its operation. For the purposes of the present invention, heat-generating components include, but are not limited to: semiconductor integrated circuits (ICs), electrochemical cells, power transistors, resistors, and electroluminescent elements, such as microprocessors, wafers for manufacturing semiconductor devices, power control semiconductors, power distribution switchgear, power transformers, circuit boards, multi-chip modules, packaged or unpackaged semiconductor devices, semiconductor integrated circuits, fuel cells, lasers (conventional diodes or laser diodes), light-emitting diodes (LEDs), and electrochemical cells, such as electrochemical cells for high-power applications (such as, for example, hybrid vehicles or electric vehicles).

[0163] For the purposes of the present invention, electronic devices include, but are not limited to, personal computers, microprocessors, servers, mobile phones, tablets, digital household appliances (such as televisions, media players, game consoles, etc.), personal digital assistants, data centers, stationary batteries and batteries in vehicles (including Li-ion batteries and other batteries used in hybrid vehicles or electric vehicles), wind turbines, train engines, or generators. Preferably, the electronic device is a hybrid vehicle or an electric vehicle.

[0164] The present invention also relates to an electronic device that includes the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20). For the purposes of the present invention, refrigerants are provided for cooling and / or heating an electronic device.

[0165] The present invention also relates to an electronic device that includes a heat-generating component and the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) for cooling and optionally heating the electronic device.

[0166] The present invention also relates to an electronic device that includes a heat-generating component, a heat exchanger, a pump, and the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20). For the purposes of the present invention, the electronic device can be any such device, including but not limited to personal computers, microprocessors, servers, mobile phones, tablets, digital household appliances (such as televisions, media players, game consoles, etc.), personal digital assistants, data centers, hybrid vehicles or electric vehicles, stationary batteries and batteries in vehicles, electric drive motors, fuel cells (such as, for example, hydrogen fuel cells), and generators, preferably where the electronic device is in a hybrid vehicle, or an electric vehicle, or a wind turbine, or a train.

[0167] For the purposes of the present invention, a heat-generating component can be any electrical component that generates heat during operation and / or during its manufacture, including electronic components that generate heat and / or are exposed to heat at high levels of heat flux. Example components that can be cooled using the refrigerants of the present invention (including Refrigerants 1 to 8 and RB1 to RB20) during operation and / or manufacture include semiconductor integrated circuits (ICs), electrochemical cells, power transistors, resistors, and electroluminescent elements, such as microprocessors, wafers for manufacturing semiconductor devices, power control semiconductors, distribution switchgear, power transformers, printed circuit boards (PCBs), multi-chip modules, packaged or unpackaged semiconductor devices, semiconductor integrated circuits, fuel cells, lasers (conventional or laser diodes), light-emitting diodes (LEDs), and electrochemical cells, for example, for high-power applications such as hybrid or electric vehicles.

[0168] Lithium-Ion Battery Cooling System

[0169] Examples of the heat management method of the present invention that can be used for cooling a lithium-ion battery will now be described in conjunction with Figure 8 including using the refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) in such methods including Heat Transfer Method 1. A vehicle battery pack having a self-contained liquid cooling system 10 includes a module 12 formed by 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-contained 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 prime mover vehicles can be provided with the liquid cooling system 10 of the present invention, where each battery cell includes active material for generating electricity from an electrochemical reaction within the internal space 16 of the container 14. The battery cells 20 are preferably stacked to form a battery cell stack 22. In the illustrated embodiment, the gap 24 between each battery cell 20 is between 0.25 mm and 0.50 mm, thereby forming a fluid channel 26 between each battery cell 20. In another embodiment, the gap 24 can be less than 0.25 mm. It should be understood that other gap sizes can be used as needed.

[0170] The composition of the present invention (including Composition 1) and the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) are disposed within the interior space 16 of the container 14, and the indicated liquid level is such that the battery assembly 18 is completely immersed in the composition / refrigerant of the present invention. The composition of the present invention (including Composition 1) and the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) contact the battery cells 20 through the fluid passage 26 formed by the gap 24.

[0171] The heating element 34 is located at the base region 36 of the container 14. The indicated heating element 34 is an electric heating element. It should be understood that other types of heating elements may be used. The heating element 34 is shown as a single element; however, a plurality of heating elements 34, such as a heating plate, may be provided.

[0172] The cooling element 38 is located at the upper region 40 of the container 14. The cooling element 38 may be a water chiller condenser having an inlet 42 and an outlet 44 that extend beyond the wall of the sealed container 14 for inputting and outputting water to the cooling element 38. In another embodiment, the cooling element 38 may be a water cooling plate. In yet another embodiment, the cooling element 38 may be a thin aluminum heat sink having external cold water traveling through the cooling element 38. The cooling element 38 may be a graphite foil impregnated with a non-conductive polymer. The cooling element may also be formed of copper.

[0173] In the illustrated embodiment, arrows "A" and "B" indicate the flow 28 of the composition of the present invention (including Composition 1) and the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20). When heating each battery cell 20 by the heating element 34, the fluid 28 (including the composition of the present invention (including Composition 1) and the refrigerant of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20)) is exposed to the front surface region 30 and the rear surface region 32 of the battery cell 20 and will boil. The heated coolant 28 will rise and flow to the top of the battery cell stack 22 to be cooled by the cooling element 38. The cooled coolant 28 will generally follow the coolant path "A" or "B" back to the base region 36. In the case where the approximate position of the coolant 28 at the boiling moment is within the fluid passage 26 of the battery cell 20 in the central region of the container 14 and toward the side 50 of the container, the coolant 28 will tend to follow the flow path "A". Similarly, if the approximate position of the dielectric coolant 28 at the boiling moment is within the fluid passage 26 of the battery cell 20 in the central region of the container 14 and toward the opposite side 52 of the container, the coolant 28 will tend to follow the flow path "B".

[0174] The coolant temperature sensor 46 is located on or near the cooling element 38. In the illustrated embodiment, the temperature sensor 46 is located in 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 can be located anywhere within the battery cell stack 22 as needed.

[0175] A coolant level sensor 48 is also provided and is located near the upper region 40 of the container 14 to measure the level of the dielectric coolant 28 (including the compositions of the present invention (including Composition 1) and the refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20)) within the container 14, thereby ensuring that the battery assembly 18 is fully immersed in the dielectric coolant 28.

[0176] Heat Dissipation Tube Cooling and Heating

[0177] Now with respect to Figure 10An example of the heat transfer method of the present invention using a heat pipe is described. This figure is a specific example of the heat pipe in the energy storage assembly 1 according to an exemplary embodiment of the present invention. The energy storage assembly 1 can be part of a motor vehicle 12 (especially a hybrid vehicle or an electric vehicle) and is provided for supplying electric power to an electric consumption device on the motor vehicle side, such as an electric drive unit (not shown). The energy storage assembly 1 includes a plurality of electrical energy storage devices. 2. The electrical energy storage devices 2 are electrically connected via electrical connection elements (not shown), especially in the form of conductive rails or conductor rails ("busbars"), i.e., connected in series or in parallel. The electrical connection elements contact corresponding electrical connectors (not shown) which are arranged on the respective exposed outer wall sections of the corresponding energy storage housings (not shown) of the parallel-aligned energy storage devices 2 arranged adjacent to each other, thereby forming an energy storage stack ("stack"). Plate-shaped spacer elements 3 are respectively arranged between the energy storage devices 2 to separate the energy storage devices and at the same time the spacer elements have heat-conducting properties. Thus, on the one hand, the spacer elements 3 provide a spacing between directly adjacent energy storage devices 2 such that the directly adjacent energy storage devices 2 are in electrical contact or mechanical contact with each other. On the other hand, due to their heat-conducting properties, the spacer elements 3 act as heat conductors to cool the energy storage devices 2 or the energy storage assembly 1 by dissipating heat especially from the contacting energy storage devices 2, or to heat the energy storage devices 2 or the energy storage assembly 1 by supplying heat especially to the contacting energy storage devices 2. A heat pipe 4 of a first heat pipe assembly 5 and a heat pipe 6 of a second heat pipe assembly 7 are provided. The heat pipes 4, 6 thus extend along this side surface of the energy storage stack and are respectively thermally coupled to the spacer elements 3. Thus, the spacer elements 3 form a thermal bridge 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 devices 2. The respective heat pipes 4 of the first heat pipe assembly 5 are arranged and aligned to be thermally coupled to a corresponding evaporation zone in which the refrigerant contained in the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be evaporated to the spacer elements 3. Thus, the heat (evaporation heat) required to evaporate the refrigerant of the present invention is removed from the spacer elements 3 or via the spacer elements 3 from the energy storage devices 2. The energy storage devices 2 including the energy storage assembly 1 can thus be cooled via the heat pipes 4 of the first heat pipe assembly 5. In addition, the corresponding condensation zone of the heat pipes 4 of the first heat pipe assembly 5 is thermally coupled to a radiator 8 in the form of a motor vehicle side heat exchanger in which the gaseous refrigerant contained in the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be condensed. Thus, the heat (condensation heat) generated during the condensation of the refrigerant of the present invention can be transferred to the radiator 8. The heat exchanger can be part of the energy storage assembly 1, i.e., belong to the energy storage assembly 1 or be associated with the energy storage assembly 1.The respective heat pipes 6 of the second heat pipe assembly 7 are arranged and aligned so as to be in thermal connection with their respective condensation zones in which the gaseous refrigerant contained in the present invention can be condensed onto the spacer element 3. Thus, heat (condensation heat) can be transferred to the spacer element 3 during the condensation of the refrigerant of the present invention or via the spacer element 3 to the energy storage device 2. Thus, the energy storage device 2 and the energy storage assembly 1 can be heated via the heat pipes 6 of the second heat pipe assembly 7. In addition, the respective evaporation zones of the heat pipes 6 of the second heat pipe assembly 7, in which the refrigerant contained in the present invention can be evaporated, are in thermal connection with a heat source 9 in the form of a functional component, i.e., for example, a charger or a control device or control electronics associated with the energy storage assembly 1. The heat (evaporation heat) required for the evaporation of the refrigerant can thus 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, 7 and their associated heat pipes 4, 6 enable a temperature control device to control the temperature of the energy storage device 2 of the energy storage assembly 1 (i.e., for heating or cooling). Heat pipes useful according to the present invention include gravity return heat pipes, capillary return heat pipes, and gravity / capillary return heat pipes.

[0178] Organic Rankine Cycle

[0179] When the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) is used in an organic Rankine cycle, it can be referred to as a working fluid.

[0180] Thus, the working fluid corresponds to the refrigerant discussed in the present application. All of the preferred features of the heat transfer fluid apply to the working fluid as described herein.

[0181] It is known that a Rankine cycle system is a simple and reliable device for converting thermal energy into mechanical energy in the form of shaft power. In an industrial environment, combustible working fluids (such as toluene and pentane) may be used, especially when the industrial environment already has a large amount of combustibles on-site in the process or in storage. However, in situations where the risks associated with the use of combustible and / or toxic working fluids are unacceptable, such as for power generation in populated areas or near buildings, it is necessary or at least highly desirable to use non-combustible and / or non-toxic refrigerants as the working fluid. There is also a drive in the industry to make these materials environmentally acceptable in terms of GWP.

[0182] The process for recovering waste heat in an organic Rankine cycle according to the present invention preferably involves pumping the liquid-phase working fluid of the present invention (including the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20)) through a boiler, where an external (waste) heat source (such as a process stream) heats the working fluid to evaporate it into saturated or superheated vapor. This vapor expands through a turbine, where the waste heat energy is converted into mechanical energy. Subsequently, the gaseous-phase working fluid is condensed into a liquid and pumped back to the boiler to repeat the regenerative cycle.

[0183] See Figure 4 , in an exemplary organic Rankine cycle system 70, the working fluid of the present invention (including the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20)) circulates between an evaporator 71 and a condenser 75, where a pump 72 and an expansion device 74 are functionally arranged therebetween. In the illustrated embodiment, an external fluid stream is guided to the evaporator 71 via an external warm conduit 76. The external warm conduit 76 can carry a fluid from a warm heat source, such as a waste heat source from an industrial process (such as power generation), flue gas, exhaust gas, a geothermal heat source, etc.

[0184] The evaporator 71 is preferably configured as a heat exchanger, which can include, for example, a series of thermally connected but fluid-isolated tubes that respectively carry a fluid from the external warm conduit 76 and a fluid from the working fluid conduit 77B. Thus, the evaporator 71 facilitates the transfer of heat QIN from the warm fluid arriving via the external warm conduit 76 to the relatively cooler (e.g., "cold") working fluid arriving from the expansion device 74 via the working fluid conduit 77B.

[0185] Thus, the working fluid of the present invention (including the fluoroethers of the present invention) is discharged from the evaporator 71, has been warmed by absorbing heat QIN, and then travels through the working fluid conduit 78A to the pump 72. The pump 72 pressurizes the working fluid, thereby further warming the fluid through an external energy input (e.g., electricity). The resulting "hot" fluid is optionally transferred via a conduit 78B to the input of the condenser 75 via a regenerator 73 as described below.

[0186] The condenser 75 is configured as a heat exchanger similar to the evaporator 71, and can include, for example, a series of thermally connected but fluid-isolated tubes that respectively carry a fluid from the cooling conduit 79 and a fluid from the working fluid conduit 78B. The condenser 75 facilitates the transfer of heat QOUT from the cooling fluid arriving via the external cooling conduit 79 to the relatively warmer (e.g., "hot") working fluid of the present invention (including the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20)) arriving from the pump 72 via the working fluid conduit 78B.

[0187] The working fluid of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) discharged from the condenser 75 has thus been cooled by the heat loss QOUT and then travels 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 do work, for example, by driving a turbine. The resulting "cold" fluid is optionally transferred via the conduit 77B to the input of the evaporator 71 via the regenerator 73 as described below, and the cycle starts again.

[0188] Therefore, the working fluid conduits 77A, 77B, 78A, and 78B define a closed loop such that the working fluid contained therein can be reused infinitely or until routine maintenance is required.

[0189] In the illustrated embodiment, the regenerator 73 can be functionally disposed between the evaporator 71 and the condenser 75. The regenerator 73 allows some heat exchange between the "hot" working fluid of the present invention (including the fluoroether of the present invention) leaving the pump 72 and the "cold" working fluid discharged from the expansion device 74, and there may be a time lag between the deposition of heat from the hot working fluid and the release of this heat to the cold working fluid. In some applications, this can increase the overall thermal efficiency of the Rankine cycle system 70.

[0190] The present invention also provides a method for converting thermal energy into mechanical energy in a Rankine cycle, the method comprising the steps of: i) evaporating the working fluid of the present invention (including the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20)) with a heat source and expanding the resulting vapor, and then ii) cooling the working fluid with a radiator to condense the vapor, wherein the working fluid is the refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20).

[0191] The mechanical work can be transmitted to an electrical device such as a generator to generate electricity.

[0192] The heat source can be provided, for example, by a heat energy source selected from industrial waste heat, solar energy, geothermal hot water, low-pressure steam, distributed power generation equipment using fuel cells, a prime mover, or an internal combustion engine. The low-pressure steam is preferably low-pressure geothermal steam or provided by a power plant powered by fossil fuels.

[0193] The heat source is preferably provided by a heat energy source selected from industrial waste heat or an internal combustion engine.

[0194] It should be understood that the heat source temperature can vary widely, for example, from about 90 °C to > 800 °C, and can depend on many factors of certain combustion gases and some fuel cells, including geographical location, time of year, etc.

[0195] The source temperature of a system based on sources such as wastewater or low-pressure steam (from, for example, plastic manufacturing plants and / or from chemical or other industrial plants, refineries) and related forms, as well as geothermal sources, can be equal to or lower than about 175 °C or equal to or lower than about 100 °C, and in some cases as low as about 90 °C or even as low as about 80 °C. The source temperature of a gaseous heat source (such as exhaust gas from a combustion process or from any heat source where subsequent treatment for removing particulate and / or corrosive substances results in a low temperature) can also be equal to or lower than 200 °C, equal to or lower than about 175 °C, equal to or lower than about 130 °C, equal to or lower than about 120 °C, equal to or lower than about 100 °C, equal to or lower than about 100 °C, and in some cases as low as about 90 °C or even as low as about 80 °C.

[0196] However, in some applications, it is preferred that the heat source has a temperature of at least about 200 °C, for example, from about 200 °C to about 400 °C.

[0197] In an alternative preferred embodiment, the heat source has a temperature of 400 °C to 800 °C, more preferably 400 °C to 600 °C.

[0198] Heat Pump

[0199] The refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be used in a high-temperature heat pump system.

[0200] See Figure 5 , in an exemplary heat pump system, a compressor 80 (such as a rotary compressor, piston compressor, screw compressor, or scroll compressor) compresses the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20), and the refrigerants of the present invention are transferred to a condenser 82 to release heat QOUT to a first location, then the refrigerants pass through an expansion device 84 to reduce the refrigerant pressure, and then the refrigerants pass through an evaporator 86 to absorb heat QIN from a second location. The refrigerants are then transferred back to the compressor 80 for compression.

[0201] The present invention provides a method of heating a fluid or a body using a high-temperature heat pump, the method comprising the steps of: (a) condensing the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) near the fluid or body to be heated, and (b) evaporating the refrigerants.

[0202] Examples of high-temperature heat pumps include heat pump tumble dryers or industrial heat pumps. It should be understood that a heat pump may include a suction line / liquid line heat exchanger (SL-LL HX). A so-called "high-temperature heat pump" refers to 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, more preferably at least about 110 °C.

[0203] Secondary Loop System

[0204] The refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) can be used as the secondary refrigerant fluid in a secondary loop system.

[0205] The secondary loop system includes a primary vapor compression system loop that uses a primary refrigerant and whose evaporator cools the secondary loop fluid. Then the secondary refrigerant fluid (including the refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20)) provides the necessary cooling for the application. The secondary refrigerant fluid should preferably be non-flammable and have low toxicity because the fluid in such loops is potentially exposed to humans near the cooled space. In other words, the refrigerants of the present invention (including each of Refrigerants 1 to 8 and RB1 to RB20) can be used as the "secondary refrigerant fluid" in a secondary loop system.

[0206] See Figure 6 , an 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 compressor, a piston compressor, a screw compressor, or a scroll compressor) compresses the primary refrigerant, which is transferred to a condenser 96 to release heat QOUT to a first location, after which the primary refrigerant passes through an expansion device 98 to reduce the refrigerant pressure, and then the primary refrigerant passes through a refrigerant / secondary fluid heat exchanger 100 to exchange heat QIN with the secondary fluid (including the fluoroether of the present invention), wherein 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 another location, for example, to absorb heat QIN-S to provide cooling to another location.

[0207] The primary fluid for the primary loop (vapor compression cycle, the external / outdoor part of the loop) can be selected from but 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.

[0208] The secondary loop system can be used in refrigeration or air conditioning applications, that is, the secondary loop system can be a secondary loop refrigeration system or a secondary loop air conditioning system.

[0209] Examples of refrigeration systems that may include a secondary loop refrigeration system (including the secondary refrigerant of the present invention (including the fluoroethers of the present invention)) include: cryogenic refrigeration systems, medium temperature refrigeration systems, commercial refrigerators, commercial freezers, industrial freezers, industrial refrigerators, and coolers.

[0210] Examples of air conditioning systems that may include a secondary loop air conditioning system that utilizes the refrigerant of the present invention (including the fluoroethers of the present invention) include mobile air conditioning systems or stationary air conditioning systems. Mobile air conditioning systems include air conditioners for road vehicles such as cars, trucks, and buses, as well as air conditioners for boats and trains. For example, where the vehicle includes a battery or power source.

[0211] Examples of stationary air conditioning systems that may include a secondary loop air conditioning system that utilizes the refrigerant of the present invention (including the fluoroethers of the present invention) include: modular or conventional single-packaged coolers, particularly positive displacement coolers, more particularly air-cooled or water-cooled direct expansion coolers; residential air conditioning systems, particularly ducted split or ductless split air conditioning systems; residential heat pumps; residential air-to-water heat pump / circulating heating systems; industrial air conditioning systems; commercial air conditioning systems, particularly packaged rooftop units or variable refrigerant flow (VRF) systems; and commercial air source, water source, or ground source heat pump systems.

[0212] According to the present invention, a particularly preferred heat transfer system is a motor vehicle air conditioning system that includes a vapor compression system (primary loop) and a secondary loop air conditioning system, where the primary loop contains HFO-1234yf as the refrigerant and the secondary loop contains the refrigerant or heat transfer composition of the present invention (including the fluoroethers of the present invention). Specifically, the secondary loop can be used to cool components in an automotive engine, such as a battery.

[0213] It should be understood that a secondary loop air conditioning or refrigeration system may include a suction line / liquid line heat exchanger (SL-LLHX).

[0214] The heat transfer fluid or heat transfer composition of the present invention that may include a secondary loop air conditioning system that utilizes the refrigerant of the present invention (including the fluoroethers of the present invention) can be used as a replacement for existing fluids.

[0215] The present invention includes a method of replacing an existing heat transfer fluid in a heat transfer system, the method comprising the steps of: (a) removing at least a portion of the existing heat transfer fluid from the system; and subsequently (b) introducing the heat transfer fluid of the present invention into the system. Step (a) may involve removing at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 50 wt%, at least about 70 wt%, at least about 90 wt%, at least about 95 wt%, at least about 99 wt%, or at least about 99.5 wt% or substantially all of the existing heat transfer fluid from the system before step (b).

[0216] The method may optionally include the step of flushing the system with a solvent after performing step (a) and before performing step (b).

[0217] For the purposes of the present invention, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be used to replace existing fluids in electronic devices, organic Rankine cycles, high-temperature heat pumps, or secondary circuits.

[0218] For example, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be used as alternatives to existing fluids such as HFC-4310mee, HFE-7100, and HFE-7200. Alternatively, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be used to replace water and glycols. The replacement can be carried out in an existing system or in a new system designed to operate with the existing fluid. Alternatively, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be used in applications that previously used existing refrigerants. Alternatively, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be used to retrofit existing refrigerants in an existing system. Alternatively, the refrigerants of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) can be used in a new system designed to work with existing refrigerants.

[0219] The present invention provides a method for replacing an existing refrigerant in a heat transfer system, the method comprising the steps of: (a) removing at least a portion of the existing refrigerant from the system, and subsequently (b) introducing a refrigerant of the present invention (including each of refrigerants 1 to 8 and RB1 to RB20) into the system. The existing refrigerant can be selected from, for example, HFC-4310mee, HFE-7100, and HFE-7200.

[0220] Step (a) may involve removing at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 50 wt%, at least about 70 wt%, at least about 90 wt%, at least about 95 wt%, at least about 99 wt%, or at least about 99.5 wt% of the existing refrigerant from the system before step (b).

[0221] The method may optionally include the step of flushing the system with a solvent after performing step (a) and before performing step (b).

[0222] Solvent and Cleaning Uses, Methods and Systems

[0223] The present invention provides solventization methods. Such methods generally include cleaning methods, etching methods, carrier solvent applications (for coating applications, lubricant deposition, silicone deposition, and other coatings, including coatings related to the coatings of medical devices, such as heparin and PTFE) using the compositions of the present invention (including Composition 1).

[0224] All such methods are included within the scope of the present invention relative to the cleaning methods. Preferred cleaning methods include vapor degreasing by contacting an article, device, or part thereof with the compositions of the present invention (including Composition 1). A variety of contaminants can be removed from a variety of articles, devices, and parts. Examples of contaminants that can be removed using the compositions of the present invention (including the fluoroethers of the present invention) include, for example, light oils, medium oils, fluorocarbon lubricants, greases, and silicones and waxes. Examples of articles, devices, and parts that can be cleaned using the compositions of the present invention (including Composition 1) include, for example, electronic components (including silicon wafers, PCBs, semiconductor surfaces), precision components (including aircraft parts and components), light oils, medium oils, fluorocarbon lubricants, greases, and silicones and waxes.

[0225] Preferred solvent vapor degreasing and desoldering methods of the present invention include immersing a contaminated substrate or part (such as a printed circuit board or a machined metal, glass, ceramic, plastic, or elastomeric part or composite material) or a portion of the substrate or part into a boiling, non-flammable liquid according to the present invention (including the compositions of the present invention (including Composition 1)), and then rinsing the part in a second tank or cleaning area by immersion or distillation spraying with a cleaning solvent, which can also be any of the compositions in the compositions of the present invention. The part is then dried by holding the cooled part in the condensing vapor until the temperature reaches equilibrium.

[0226] Solvent cleaning of various types of parts is generally carried out in batch, lift-assisted batch, conveyor batch, or in-line conveyor-type degreasing and desoldering equipment. Parts can also be cleaned in open desoldering or degreasing equipment. In both types of equipment, the inlet end and / or the outlet end of the equipment can be in open communication with the surrounding environment and the solvent within the equipment. To minimize the loss of solvent from the equipment by convection or diffusion, conventional practices in the art are used.

[0227] The present invention includes a solvent composition, which comprises a combination of the composition of the present invention (including Composition 1) and a co-solvent. The co-solvent can be selected from the group consisting of: hexafluoroisopropyl ethyl ether, hexafluoroisopropyl methyl sulfide, 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).

[0228] Electrolyte Formulations and Batteries

[0229] The present invention also provides an electrolyte formulation and a battery containing the electrolyte formulation. The electrolyte formulation comprises the composition of the present invention (including Composition 1). Generally speaking, the electrolyte formulation comprises: (a) an electrolyte; (b) an organic solvent for the electrolyte; and (c) an additive, which is included in the formulation to provide or improve the desired properties of the electrolyte formulation and / or the battery containing the electrolyte. The composition of the present invention (including Composition 1) can be included in the formulation as a solvent (or co-solvent) for the electrolyte and / or as an additive.

[0230] Therefore, the present invention provides an electrolyte formulation, which comprises: a salt, preferably a lithium ion salt; a solvent for the salt, the solvent comprising the composition of the present invention (including Composition 1), with or without a co-solvent; and one or more additives different from the compounds of the present invention. The present invention also provides an electrolyte formulation, which comprises: (a) an electrolyte, preferably a lithium ion electrolyte; (b) a solvent for the lithium ion electrolyte; and (c) an additive, the additive comprising the composition of the present invention (including Composition 1), with or without additional additives.

[0231] The present invention generally also provides a battery, and in particular a rechargeable lithium ion battery, which comprises an electrolyte formulation containing the composition of the present invention (including Composition 1). Exemplary rechargeable lithium ion batteries are shown in their Figure 9 in which a cathode and an anode are shown, as well as the electrolyte formulation of the present invention that facilitates the flow of lithium ions between the cathode and the anode.

[0232] Although it is expected that the electrolyte formulations of the present invention can generally be used in batteries, in a preferred embodiment, the electrolyte formulation comprises a lithium ion electrolyte that can be used in rechargeable batteries. Non-limiting examples of lithium salts that can constitute the electrolyte portion of the formulation include: LiPF 6 、LiAsF 6 、LiCIO4 *LiBF 4 、LiBC 4 Og(LiBOB), LiBCO 4 F,(LiODFB), LiPF 3 (C 2 F 5 ) 3 (LiFAP), LiBF 3 (C 2 F 5 )LiPF 3 (C,F 5 ) 3 (LiFAB), LiN,(CF 3 SO,)LiN(C,F 5 SO,), LiCF 3 S0 3 、LiC(CF 3 SO) 3 、LiPF 4 (CF 3 ) 2 、LiPF3(CF 3 ) 3 、LiPF 3 (iSO-C 3 C 7 ) 3 、LiPF 5 (iso-C 3 F 7 )。The total salt concentration can vary according to the specific needs of the application, and in some embodiments, the electrolyte can be present in the formulation in an amount between about 0.3 M and about 2.5 M or about 0.7 M to about 1.5 M.

[0233] Examples

[0234] Example 1 - Synthesis of HFPOHFP from HFP and HFIP

[0235] Synthesize HFPOHFP from HFP and HFIP according to the following steps.

[0236] 250 mL of DMF and 10 g of cesium carbonate were added to a 3-neck 500 mL round-bottom jacketed flask equipped with a mechanical stirrer, a dry ice condenser, a gas distributor (for HFP), and a temperature sensor. The condenser outlet was attached to a nitrogen tee. Cooling water was turned on before adding 125 mL of HFIP. At this point, a slight exotherm was observed. The reaction was cooled to below 25 °C. Then, 200 g of HFP was added over a 60-minute period using the distributor and a needle valve such that the temperature of the reaction mixture did not exceed 25 °C. The reaction exotherm was observed and it turned light yellow towards the end of the addition. Once the reaction was nearly complete, the exotherm slowed down and the reaction temperature dropped rapidly. The reaction mixture was decanted from the flask and filtered, and then rotary evaporated at 45 °C and 60 to 70 Torr. The reboiler heavy material was poured into water and the lower layer (colorless liquid) was separated to give 325.0 g (81% yield, GC 83.39%). Alternatively, the reaction mixture was decanted and completely rotary evaporated under the same conditions to give 323.8 g (80.6% yield, GC 82.92%). Then the material was distilled and combined, and a total of 562.8 g of material with over 95% was obtained by GC analysis.

[0237] The reagents used and their physical properties, as well as the molecular weight, boiling point, and density of the resulting HFPOHFP, are shown in Table E1A below.

[0238] Table E1A

[0239]

[0240] The HFPOHFP was also tested using an Ubbelohde viscometer according to the procedure described in ASTM D2196 to determine its density over a temperature range, and the results of this test are reported in Table E2 below:

[0241] Table E1B

[0242] Temperature (°C) Viscosity (cSt) -59.30 5.38 -9.40 0.99 0.10 0.80 10.57 0.68 21.12 0.56 31.59 0.49 41.83 0.42 51.84 0.38 61.75 0.34

[0243] As can be seen from the above data, the compositions of the present invention (including Refrigerants 1 to 8) are capable of exhibiting a combination of properties including viscosity, dielectric constant, and boiling point that provide unexpected advantageous performance over the temperature ranges of interest in many of the preferred heat transfer methods of the present invention, including Heat Transfer Method 1.

[0244] Example 2 - Synthesis of TFE / HFP from HFP and TFE

[0245] Synthesis of TFE / HFP from HFP and TFE according to the following procedure. 250 mL of DMF and 10 g of cesium carbonate were added to a 3-necked 500 mL round-bottomed jacketed flask equipped with a mechanical stirrer, a dry ice condenser, a gas distributor (for HFP), and a temperature sensor. The condenser outlet was attached to a nitrogen three-way valve. Cooling water was turned on before adding 86 mL of TFE. At this time, a slight exotherm was observed. The reaction was cooled to below 25 °C. Then, 200 g of HFP was added over a 60-minute period using the distributor and a needle valve such that the temperature of the reaction mixture did not exceed 25 °C. The reaction exotherm was observed and it turned light yellow near the end of the addition. Once the reaction was almost complete, the exotherm slowed down and the reaction temperature dropped rapidly. The reaction mixture was decanted from the flask and filtered, and then rotary evaporated at 45 °C and 60 to 70 Torr. The reboiler heavy matter was poured into water and the lower layer (colorless liquid) was separated to obtain 325.0202 g (801% yield, GC 8385.39%). Alternatively, the reaction mixture was decanted and completely rotary evaporated under the same conditions to obtain 323.8 g (80.6% yield, GC 82.92%). Then the material was distilled and combined, and a total of 562.8 g of material with over 95% was obtained using GC with a very sensitive method.

[0246] Example 3A - Method and Use of Refrigerant 1 in the Manufacture of Electronic Components

[0247] As part of the manufacturing process, an electronic component or a part thereof that is cooled while being processed during manufacturing (such as, for example, in the etching of a silicon wafer as shown, for example) is brought into direct or indirect contact with refrigerant 1 to effect heat transfer therebetween (to and / or from the electronic component). Effective temperature control is provided. Figure 11 As part of the manufacturing process, an electronic component or a part thereof that is cooled while being processed during manufacturing (such as, for example, in the etching of a silicon wafer as shown, for example) is brought into direct or indirect contact with refrigerant 1 to effect heat transfer therebetween (to and / or from the electronic component). Effective temperature control is provided.

[0248] Example 3B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Electronic Components

[0249] Example 3A was repeated to cool the electronic component while being processed, except that as part of the manufacturing process, each of refrigerants 2 to 8 and each of RB1 to RB2 were used to effect heat transfer therebetween (to and / or from the electronic component). Effective temperature control is provided.

[0250] Example 4A - Method and Use of Refrigerant 1 in the Manufacture of Semiconductor Integrated Circuits (ICs)

[0251] As part of the manufacturing process, a semiconductor integrated circuit and / or a part thereof that is cooled while being processed during manufacturing is brought into direct or indirect contact with refrigerant 1 to effect heat transfer therebetween (to and / or from the semiconductor integrated circuit and / or a part thereof). Effective temperature control is provided.

[0252] Example 4B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Semiconductor Integrated Circuits (ICs)

[0253] Repeat Example 4A to cool the semiconductor integrated circuit while processing, except that as part of the manufacturing process, each of Refrigerants 2 to 8 and each of RB1 to RB2 are used to transfer heat therebetween (to and / or from the semiconductor integrated circuit). Effective temperature control is provided.

[0254] Example 5A - Method and Use of Refrigerant 1 in the Manufacture of Electrochemical Cells

[0255] As part of the manufacturing process, an electrochemical cell and / or a part thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the electrochemical cell and / or a part thereof). Effective temperature control is provided.

[0256] Example 5B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Electrochemical Cells

[0257] Repeat Example 5A to cool the electrochemical cell while processing, except that as part of the manufacturing process, each of Refrigerants 2 to 8 and each of RB1 to RB2 are used to transfer heat therebetween (to and / or from the electrochemical cell). Effective temperature control is provided.

[0258] Example 6A - Method and Use of Refrigerant 1 in the Manufacture of Power Transistors

[0259] As part of the manufacturing process, a power transistor and / or a part thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the electrochemical cell and / or a part thereof). Effective temperature control is provided.

[0260] Example 6B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Electrochemical Cells

[0261] Repeat Example 6A to cool the power transistor while processing, except that as part of the manufacturing process, each of Refrigerants 2 to 8 and each of RB1 to RB2 are used to transfer heat therebetween (to and / or from the power transistor). Effective temperature control is provided.

[0262] Example 7A - Method and Use of Refrigerant 1 in the Manufacture of Electroluminescent Elements

[0263] As part of the manufacturing process, an electroluminescent element and / or a part thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the electroluminescent element and / or a part thereof). Effective temperature control is provided.

[0264] Example 7B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Electroluminescent Elements

[0265] Repeat Example 7A to cool the electroluminescent element while processing, except that as part of the manufacturing process, each of Refrigerants 2 to 8 and each of RB1 to RB2 are used to transfer heat therebetween (to and / or from the electroluminescent element). Effective temperature control is provided.

[0266] Example 8A - Method and Use of Refrigerant 1 in the Manufacture of Microprocessors

[0267] As part of the manufacturing process, the microprocessor and / or a part thereof that is cooled while being processed during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the microprocessor and / or a part thereof). Effective temperature control is provided.

[0268] Example 8B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Microprocessors

[0269] Repeat Example 8A to cool the microprocessor while processing, except that as part of the manufacturing process, each of Refrigerants 2 to 8 and each of RB1 to RB2 are used to transfer heat therebetween (to and / or from the microprocessor). Effective temperature control is provided.

[0270] Example 9A - Method and Use of Refrigerant 1 in the Manufacture of Semiconductor Wafers

[0271] As part of the manufacturing process, the semiconductor wafer and / or a part thereof that is cooled while being processed during manufacturing (such as, for example, in the etching of a silicon wafer as shown, for example, Figure 11 is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the semiconductor wafer and / or a part thereof). Effective temperature control is provided.

[0272] Example 9B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Semiconductor Wafers

[0273] Repeat Example 9A to cool the semiconductor wafer while processing, except that as part of the manufacturing process, each of Refrigerants 2 to 8 and each of RB1 to RB2 are used to transfer heat therebetween (to and / or from the semiconductor wafer). Effective temperature control is provided.

[0274] Example 10A - Method and Use of Refrigerant 1 in the Manufacture of Power Control Semiconductors

[0275] As part of the manufacturing process, the power control semiconductor and / or a part thereof that is cooled while being processed during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the power control semiconductor and / or a part thereof). Effective temperature control is provided.

[0276] Example 10B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Power Control Semiconductors Use

[0277] Repeat Example 10A to cool the power control semiconductor while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the power control semiconductor). Effective temperature control is provided.

[0278] Example 11A - Method and Use of Refrigerant 1 in the Manufacture of Distribution Switchgear

[0279] As part of the manufacturing process, the power distribution switchgear and / or a part thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the power distribution switchgear and / or a part thereof). Effective temperature control is provided.

[0280] Example 11B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Power Control Semiconductors Use

[0281] Repeat Example 11A to cool the power distribution switchgear while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the power distribution switchgear). Effective temperature control is provided.

[0282] Example 12A - Method and Use of Refrigerant 1 in the Manufacture of Power Transformers

[0283] As part of the manufacturing process, the power transformer and / or a part thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the power transformer and / or a part thereof). Effective temperature control is provided.

[0284] Example 12B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in the Manufacture of Power Transformers

[0285] Repeat Example 12A to cool the power transformer while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the power distribution switchgear). Effective temperature control is provided.

[0286] Example 13A - Method and Use of Refrigerant 1 in Printed Circuit Board (PCB) Manufacturing

[0287] As part of the manufacturing process, the printed circuit board (PCB) and / or a part thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the printed circuit board (PCB) and / or a part thereof). Effective temperature control is provided.

[0288] Example 13B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in Printed Circuit Board (PCB) Manufacturing

[0289] Repeat Example 13A to cool a printed circuit board (PCB) while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the printed circuit board (PCB)). Effective temperature control is provided.

[0290] Example 14A - Method and Use of Refrigerant 1 in Multi-Chip Module (MCM) Manufacturing

[0291] As part of the manufacturing process, an MCM and / or a portion thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the MCM and / or a portion thereof). Effective temperature control is provided.

[0292] Example 14B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in MCM Manufacturing

[0293] Repeat Example 14A to cool an MCM while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the MCM). Effective temperature control is provided.

[0294] Example 15A - Method and Use of Refrigerant 1 in Packaged Semiconductor Device (PSCD) Manufacturing

[0295] As part of the manufacturing process, a PSCD and / or a portion thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the PSCD and / or a portion thereof). Effective temperature control is provided.

[0296] Example 15B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in PSCD Manufacturing

[0297] Repeat Example 15A to cool a PSCD while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the PSCD). Effective temperature control is provided.

[0298] Example 16A - Method and Use of Refrigerant 1 in Unpackaged Semiconductor Device (USCD) Manufacturing

[0299] As part of the manufacturing process, a USCD and / or a portion thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the USCD and / or a portion thereof). Effective temperature control is provided.

[0300] Example 16B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in USCD Manufacturing

[0301] Repeat Example 16A to cool the USCD while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the USCD). Effective temperature control is provided.

[0302] Example 18A - Method and Use of Refrigerant 1 in Fuel Cell Manufacturing

[0303] As part of the manufacturing process, a fuel cell and / or a portion thereof that is cooled while being processed during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the fuel cell and / or a portion thereof). Effective temperature control is provided.

[0304] Example 18B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in Fuel Cell Manufacturing

[0305] Repeat Example 18A to cool the fuel cell while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the fuel cell). Effective temperature control is provided.

[0306] Example 19A - Method and Use of Refrigerant 1 in Laser Manufacturing

[0307] As part of the manufacturing process, a laser and / or a portion thereof that is cooled while being processed during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the laser and / or a portion thereof). Effective temperature control is provided.

[0308] Example 19B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in Laser Manufacturing

[0309] Repeat Example 19A to cool the laser unit while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the laser). Effective temperature control is provided.

[0310] Example 20A - Method and Use of Refrigerant 1 in Light-Emitting Diode (LED) Manufacturing

[0311] As part of the manufacturing process, an LED and / or a portion thereof that is cooled while being processed during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the LED and / or a portion thereof). Effective temperature control is provided.

[0312] Example 20B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in LED Manufacturing

[0313] Repeat Example 20A to cool the LED while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the LED). Effective temperature control is provided.

[0314] Example 21A - Method and Use of Refrigerant 1 in Electrochemical Cell (EC) Manufacturing

[0315] As part of the manufacturing process, the EC and / or a portion thereof that is cooled while processing during manufacturing is in direct or indirect contact with Refrigerant 1 to transfer heat therebetween (to and / or from the EC and / or a portion thereof). Effective temperature control is provided.

[0316] Example 21B - Method and Use of Refrigerants 2 to 8 and RB1 to RB20 in EC Manufacturing

[0317] Repeat Example 21A to cool the EC while processing, except that as part of the manufacturing process, each of Refrigerants 2 through 8 and each of RB1 through RB2 are used to transfer heat therebetween (to and / or from the EC). Effective temperature control is provided.

[0318] It should be understood that the foregoing description is merely illustrative of the present disclosure. Without departing from the present disclosure, those skilled in the art may devise various alternative and modified forms. Accordingly, the present disclosure is intended to cover all such alternatives, modifications, and variations that fall within the scope of the appended claims.

Claims

1. A method of manufacturing an electronic device or component, the method comprising: a. providing at least a portion of an electronic device and / or a component of an electronic device during a manufacturing process; b. providing a refrigerant comprising 2-(1,1,2,3,3,3-hexafluoropropoxy)-1,1,1,3,3,3-hexafluoropropane (HFPOHFP); c. directly and / or indirectly transferring heat between the electronic device and / or the component of the electronic device when manufacturing the device or component.

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 wt% 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 wt% 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 wt% 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 wt% 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 consists essentially of the 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 consists of the 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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