EP4584820A1 - Compositions comprising fluorine substituted ethers and methods and uses including same - Google Patents

Abstract

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

COMPOSITIONS COMPRISING FLUORINE SUBSTITUTED ETHERS AND METHODS AND USES INCLUDING SAME

CROSS REFERENCE

[0001] The present application is related to and claims the priority benefit of U.S. Provisional Application No. 63/415679, filed October 13, 2022, which is incorporated by reference herein in its entirety.

FIELD

[0002] The present disclosure is related to fluorine substituted ethers and uses of same in various applications, including as heat transfer fluids used in connection with the manufacture of semiconductor devices.

BACKGROUND

[0003] There continues to be a need for inert fluorinated fluids which have low global warming potential while providing high thermal stability, low toxicity, nonflammability, good solvency, and a wide operating temperature range to meet the requirements of various applications.

[0004] Applicants have come to appreciate that many challenging issues are associated with the development of new compounds and compositions for use in many important applications. In particular, applicants have come to appreciate the need for compositions, methods and systems which are at once environmentally acceptable (low GWP and low ODP), non-flammable, have low or no toxicity, and have one or more properties needed for the particular application. For example, refrigerants should provide the appropriate heat transfer properties over the temperature of use for particular heat transfer applications, and they should also have an appropriately low dielectric constant if the heat transfer application involves exposure or potential exposure of the refrigerant to electronic equipment or components. One example of such a use which has a continuing need for improved refrigerants is the transfer of heat needed to manage/control the temperature of electronic components, devices and articles during the steps used to manufacture and fabricate same. This is a substantial technical challenge since the refrigerant will frequently need to operate effectively over a relatively wide range of processing conditions, including process temperatures, and during potential exposure to electronics during said processing.

Examples of electronic manufacturing processes that experience thermal management challenges include the etching, rapid thermal annealing (RTA) and the like of semiconductor integrated circuitry, especially as the line width of such circuitry continues to decrease. These manufacturing challenges include an increasing need to achieve effective and relatively precise temperature control of certain of the fluids and/or components used in the manufacturing process. See for example U.S. Patent No. 5,904,572 (relating to wet etching processes), U.S. 2005/0155555 (relating to vapor deposition in semiconductor manufacture) and U.S. 2007/0117362 (relating to RTA), each of which is incorporated herein by reference. These challenges are intensified because it is also required in certain electronics cooling applications that the viscosity of the refrigerant fluid being used to manage the temperature of the electronic component has a sufficiently low viscosity in the operating temperature range of the refrigerant fluid to allow the fluid to be circulated and to maintain its desired heat transfer properties.

[0005] Vapor phase soldering is another example of an electronics manufacturing process that utilizes refrigerants to help manage processing temperatures. In this application, high temperatures are used and accordingly the heat transfer fluid must be suitable for high temperature exposure (e.g., up to 250° C). Currently, perfluoropolyethers (PFPE, that is, compounds that have only carbon, oxygen and fluorine) are commonly used as the heat transfer fluids in this application. Although many PFPEs have adequate thermal stability for these high temperatures, they are environmentally persistent with extremely long atmospheric lifetimes which, in turn, gives rise to very high global warming potentials (GWPs).

[0006] Another need for improved refrigerants occurs in connection with the manufacture and/or operation of small electronic devices. There has been a continuing desire to miniaturize electronic components while adding functionality, and this increases the thermal power density of the device while in operation, thus making cooling of the electronics components within such devices more challenging. As a general rule, increases in computational power within desktop computers, data centers, telecommunication centers and the like results in an increase in the heat output when such devices are operating, again making thermal management of electronic devices during manufacture and/or operation increasingly important and increasingly more difficult and demanding.

[0007] Another example of the challenge in providing refrigerants for thermal management is the increasing use of electronic vehicles, including particularly, cars, trucks, motorcycles and the like. In electric vehicles the thermal management function is especially important and challenging for several reasons, including the criticality of cooling and/or heating the batteries to be within a relatively narrow temperature range and in a way that is reliable, efficient and safe, and the challenge to provide effective thermal battery management is becoming greater as the demand for battery-operated vehicles with greater range and faster charging increases.

[0008] The efficiency and effectiveness of batteries, especially the batteries that provide the power in electronic vehicles, is a function of the operating temperature at which they operate. Thus, thermal management systems must frequently be able to do more than simply remove heat from the battery during operation and/or charging - it must be able to effect cooling in a relatively narrow temperature range using equipment that is as low cost as possible and as light weight as possible. This results in the need for a refrigerant in such systems that possess a difficult-to-achieve combination of physical and performance properties. Furthermore, in some important applications the thermal management system must be able to add heat to the battery, especially as the vehicle is started in cold weather, which adds further to the difficulty of discovering and developing /obtaining compounds and/or compositions effective in such systems, not only from a thermal performance standpoint, but also a myriad of other standpoints, including environmental, safety (flammability and toxicity), dielectric properties, and others.

[0009] As a particular example of the importance of dielectric constant, one frequently used system for the thermal management of electric vehicle batteries involves immersing the battery in the fluid used for thermal management. Such systems add the additional constraint that the fluid used in such systems must be electronically compatible with the intimate contact with the battery, or other electronic device or component, while the battery or device is in operation. In general, this means the fluid must not only be non-flammable, but it must also have a low electrical conductivity and a high level of stability while in contact with the battery or other electronic component(s) while the component(s) are operating and at the relatively high temperatures existing during operation. Applicants have come to appreciate the desirability of such properties even in indirect cooling of operating electronic devices and batteries because leakage of any such fluid may result in contact with operating electronic components.

[0010] Water/glycol combinations have been commonly used for battery cooling, including immersive cooling, and other classes of materials, including some chlorofluorocarbons, fluorohydrocarbons, chlorohydrocarbons and hydrofluoroethers, have been mentioned for possible use. See, for example, US 2018/0191038.

[0011] US 2023/0200010 discloses the use of certain fluorinated ethers for cooling of electronic equipment by at least partially immersing the electronic equipment in the fluorine-based fluid, which is said to have a boiling point of from 50°C to 60°C.

[0012] JP 2005/047856 discloses the use of several fluorinated ether compounds for use as a refrigerant, cleaning agent and the like.

[0013] Fluorinated ether compounds according to the formula

(F₃C)₂CH“O“CH,_:F_2.rs-“CH F_3.ryi

[0014] , where n is 1 or 2, and where m is any integer of 0 to 3 when n is 1 , but when n is 2, then m is 0 or 2 have been suggested for use as solvents, particularly for various fluorine-containing polyethers. See JP202105950. This document indicates that an embodiment of the above formula that is said to have a 3 - 1 configuration (understood to mean that m=3 and n=1 ) have additional uses, including as a draining agent, blowing agent, heat transfer media and fire extinguishing agent, although no such uses are specifically described or exemplified.

[0015] Thus, applicants have come to appreciate the need, among the other needs described herein, for thermal management methods and systems which use a refrigerant which is environmentally acceptable (relatively low GWP and low ODP), is non-flammable, has low or no toxicity, and has excellent thermal properties that provide effective cooling and/or heat, especially in electronics and semiconductor manufacturing processes that involve relatively high temperatures and/or for use to maintain process conditions in relatively narrow temperature range(s). For example, applicants have found that fluids that have relatively low boiling points (e.g., below about 60°C) are not desirable in many applications involving the manufacture of electronic components, as explained further hereinafter.

SUMMARY

[0016] The present invention includes compositions comprising 2-(1 ,1 , 2, 3,3,3- hexafluoropropoxy)-1 ,1 ,1 ,3,3,3-hexafluoropropane (hereinafter sometimes referred to herein as “HFPOHFP”). Compositions according to this paragraph are sometimes referred to herein for convenience as Composition 1A.

[0017] The present invention includes compositions comprising 1 , 1 ,1 , 2,3,3, - hexafluoro-3-(2,2,2-trifluoroethoxy)propane, or a combination of the foregoing. Compositions according to this paragraph are sometimes referred to herein for convenience as Composition 1 B.

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

[0019] The present invention includes refrigerants comprising HFPOHFP. Refrigerants according to this paragraph are sometimes referred to herein for convenience as Refrigerant 1.

[0020] The present invention includes refrigerants comprising at least about 10% by weight of HFPOHFP. Refrigerants according to this paragraph are sometimes referred to herein for convenience as Refrigerant 2.

[0021] The present invention includes refrigerants comprising at least about 50% by weight of HFPOHFP. Refrigerants according to this paragraph are sometimes referred to herein for convenience as Refrigerant 3. [0022] The present invention includes refrigerants comprising at least about 75% by weight of HFPOHFP. Refrigerants according to this paragraph are sometimes referred to herein for convenience as Refrigerant 4.

[0023] The present invention includes refrigerants comprising at least about 90% by weight of HFPOHFP. Refrigerants according to this paragraph are sometimes referred to herein for convenience as Refrigerant 5.

[0024] The present invention includes refrigerants consisting essentially of HFPOHFP. Refrigerants according to this paragraph are sometimes referred to herein for convenience as Refrigerant 6.

[0025] The present invention includes refrigerants consisting of HFPOHFP. Refrigerants according to this paragraph are sometimes referred to herein for convenience as Refrigerant 7.

[0026] The present invention includes refrigerants comprising 1 ,1 ,1 ,2,3,3,- hexafluoro-3-(2,2,2-trifluoroethoxy)propane (hereinafter sometimes referred to herein as “TFE/HFP”). Refrigerants according to this paragraph are sometimes referred to herein for convenience as Refrigerant 8.

[0027] The present invention includes methods for synthesizing a fluoroether from a fluoroalkene and a fluoroalcohol comprising reacting a fluoroalcohol with a fluoroalkene in the presence of a catalyst to provide the fluoroether. Methods according to this paragraph are sometimes referred to herein for convenience as Synthesis Methods 1 .

[0028] The present invention includes methods of cooling and/or heating an operating electronic device and/or an electronic component, device or article during the process of manufacture thereof comprising: providing a refrigerant comprising HFPOHFP, including each of Refrigerants 1 - 7; and thermally connecting said electronic component, device or article with said refrigerant to heat and/or cool said electronic component, device or article, preferably including by immersing at least a portion of said electronic component, device or article in said refrigerant. Methods according to this paragraph are sometimes referred to herein for convenience as Heat Transfer Method 1A. [0029] The present invention includes methods of cooling and/or heating an an electronic component, device or article during the process of manufacture thereof comprising: providing a refrigerant comprising HFPOHFP, including each of Refrigerants 1 - 7; and thermally connecting said electronic component, device or article with said refrigerant to heat and/or cool said electronic component, device or article during said process of manufacturing said electronic component, device or article. Methods according to this paragraph are sometimes referred to herein for convenience as Heat Transfer Method 1 B.

BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The above mentioned and other features of the disclosure, and the manner of attaining them, will become more apparent and the disclosure itself will be better understood by reference to the following description of embodiments of the disclosure taken in conjunction with the accompanying drawings.

[0031] Figure 1 is a schematic representation of a thermal management system of the present invention.

[0032] Figure 2A is a schematic representation of a first exemplary immersion cooling system according to the present invention.

[0033] Figure 2B is a schematic representation of a second exemplary immersion cooling system according to the present invention.

[0034] Figure 3 is a schematic illustration of a battery thermal management system according to one embodiment of the present invention.

[0035] Figure 4 is a photograph showing a battery thermal management system according to one embodiment of the present invention.

[0036] Figure 5 is a schematic diagram of an exemplary organic Rankine cycle.

[0037] Figure 6 is a schematic diagram of an exemplary heat pump.

[0038] Figure 7 is a schematic diagram of an exemplary secondary loop system.

[0039] Figure 8 is a semi-schematic drawing of one example of a lithium-ion battery cooling system using a composition of the present invention.

[0040] Figure 9 is a semi-schematic drawing of one example of a lithium-ion battery having an electrolyte formulation of the present invention. [0041] Figure 10 is a semi-schematic drawing of a heat pipe using a heat transfer composition of the present invention.

[0042] Figure 11 is a side cross-sectional view of a conventional wet-etching station.

DETAILED DESCRIPTION

I. Definitions

[0043] The terms “R-1132(E)”, “HFO-1132(E)” and “transHFO-1132(E)” each means the trans isomer of 1 ,2-difluorethylene.

[0044] The terms “R-1132a” and “HFO-1132a” each means 1 ,1 -difluoroethylene.

[0045] The terms “R-1234yf” and “HFO-1234yf” mean 2,3,3,3-tetrafluoropropene.

[0046] The terms “R-1234ze(E)” and “HFO-1234ze(E)” means the trans isomer of 1 ,3,3,3-tetrafluoropropene.

[0047] The terms “R-1233zd(E)” and “HFCO-1233zd(E)” mean the trans isomer of 1 -chloro-3,3,3-trifluoropropene.

[0048] The terms “R-1233zd(Z)” and “HFCO-1233zd(Z)” mean the cis isomer of 1 -chloro-3,3,3-trifluoropropene.

[0049] The terms “R-1224yd(E)” and “HFCO-1224yd(E)” mean the trans isomer of 1 -chloro-2,3,3,3-tetrafluoropropane.

[0050] The terms “R-1224yd(Z)” and “HFCO-1224yd(Z)” mean the cis isomer of 1 -chloro-2,3,3,3-tetrafluoropropane.

[0051] The terms “R-1336mzz(E)” and “HFO-1336mzz(E)” mean the trans isomer of 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

[0052] The term “HFE-7000” means 1 -methoxyheptafluoropropane (C3F7OCH3).

[0053] The term “HFE-7100” means 1 -methoxy-nonafluorobutane (C4F9OCH3).

[0054] The term “HFE-7200” means ethoxy-nonafluorobutane (C4F9OC2H5).

[0055] The term “HFE-7300” means 1 ,1 ,1 ,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- trifluoromethylpentane.

[0056] The term “HFE-7500” means 2-trifluoromethyl3- ethoxydodecofluorohexane. [0057] As used herein, reference to a defined group, such as “RB1 - RB2” (see Table 4 below) refers to each refrigerant blend within that group, including wherein a definition number includes a suffix. Thus, reference to “RB1 - RB2” includes reference to each RB1 A, RB1 B, etc. and RB2A, RB2B, etc.

[0058] The names of compounds as used herein with corresponding chemical names and chemical formulas are provided below in Table 1 .

Table 1

[0059] “Electronic Device”, and related word forms, means a device, or a component of a device, which is in the process of performing its intended function by receiving, and/or transmitting and/or producing electrical energy and/or electronic signals. Thus, the term “operating electronic device” as used herein includes, for example, a battery which is in the process of providing a source of electrical energy to another component and also a battery which is being charged or recharged, for example.

[0060] The term “Refrigerant” and related word forms means a fluid (liquid or gas) which is used to transfer heat or energy to (for heating) and/or from (for cooling) a fluid, article or device.

[0061] “Operating Electronic Device”, and related word forms, means a device, or a component of a device, which is in the process of performing its intended function by receiving, and/or transmitting and/or producing electrical energy and/or electronic signals. Thus, the term “operating electronic device” as used herein includes, for example, a battery which is in the process of providing a source of electrical energy to another component and also a battery which is being charged or recharged.

[0062] “Thermal contact”, and related forms thereof, includes direct contact with the surface and indirect contact though another body or fluid which facilitates the flow of heat between the surface and the fluid.

[0063] “Thermal Conductivity” refers to the breakdown voltage in kV as measured in accordance with ASTM D7896-19.

[0064] “Global Warming Potential (“GWP”)” was developed to allow comparisons of the global warming impact of different gases. It is a measure of how much energy the emission of one ton of a gas will absorb over a given period of time, relative to the emission of one ton of carbon dioxide. The larger GWP, the more that a given gas warms the Earth compared to CO2 over that time period. The time period usually used for GWP is 100 years. GWP provides a common measure, which allows analysts to add up emission estimates of different gases.

[0065] “LC50” is a measure of the acute toxicity of a compound. The acute inhalation toxicity of a compound can be assessed using the method described in the OECD Guideline for Testing of Chemicals No. 403 "Acute Inhalation Toxicity" (2009), Method B.2. (Inhalation) of Commission Regulation (EC) No. 440/2008.

[0066] The term “AMES-negative” refers to a compound or composition which returns a negative result when tested under the Ames test as specified in the Toxic Substances Control Act of the United States. [0067] “Flash Point” refers the lowest temperature at which vapors of the liquid will keep burning after the ignition source is removed as determined in accordance with ASTM D3828-16a.

[0068] “Non-flammable” in the context of heat transfer compositions, including thermal management composition or fluid, means compounds or compositions which do not have a flash point below 100°F (37.8°C) in accordance with NFPA 30: Flammable and Combustible Liquid Code. The flash point of a thermal management composition or fluid refers to the lowest temperature at which vapors of the composition will keep burning after the ignition source is removed as determined in accordance with ASTM D3828-16a.

[0069] In the context of a refrigerant composition, a compound or composition which is non-flammable and low or no-toxicity would be classified as “A1 ” by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and described in Appendix B1 to ASHRAE Standard 34-2016.

[0070] “No toxicity” or “low toxicity” means a fluid classified as class “A” by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and described in Appendix B1 to ASHRAE Standard 34-2016.

[0071] “Capacity” is the amount of cooling provided, in BTUs/hr., by the refrigerant in the refrigeration system. This is experimentally determined 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 the measurement of the pressure and temperature of the refrigerant. The capacity of the refrigeration system relates to the ability to maintain an area to be cooled at a specific temperature. The capacity of a refrigerant represents the amount of cooling or heating that it provides and provides some measure of the capability of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity will deliver more cooling or heating power.

[0072] “Coefficient of Performance” (hereinafter “COP”) is a universally accepted measure of refrigerant performance, especially useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration engineering, this term expresses the ratio of useful refrigeration or cooling capacity to the energy applied by the compressor in compressing the vapor and therefore expresses the capability of a given compressor to pump quantities of heat for a given volumetric flow rate of a heat transfer fluid, such as a refrigerant. In other words, given a specific compressor, a refrigerant with a higher COP will deliver more cooling or heating power. One means for estimating COP of a refrigerant at specific operating conditions is 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).

[0073] “Vapor Degreasing” means a surface-cleaning process that uses solvent vapors to wash oils and other contaminants off of articles or parts of articles.

[0074] “Dielectric Constant” means the dielectric constant as measured in accordance with ASTM D150-1 1 at room temperature at 20 giga hertz (GHz) (unless some other test method, temperature and giga hertz is specifically mentioned).

[0075] “Dielectric Strength” refers to the breakdown voltage in kV as measured in accordance with ASTM D87-13, Procedure A, with the modification that the spacing between the electrodes is 2.54 mm and the rate of rise was 500 V/sec.

[0076] As used herein, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise.

[0077] As used herein, the recitation of numerical ranges 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).

[0078] Unless otherwise indicated, all numbers expressing quantities or ingredients, measurement of properties and so forth used in the specification and embodiments 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 listing of embodiments can 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 light of the number of reported significant digits and by applying ordinary rounding techniques. [0079] As used herein, the phrase “within any range encompassed by 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 the values are in the lower part of the listing or in the higher part of the listing. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.

II. Synthesis from Fluoroalkenes and Fluoroalcohols

[0080] 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 below in Scheme 1.

Scheme 1

Synthesis of HFPOHFP from HFIP and HFP FIX THE SCHEME

[0081] The synthesis of 1 ,1 ,1 ,2,3,3,-hexafluoro-3-(2,2,2-trifluoroethoxy)propane (“TFE/HFP”) from HFP and TFE is shown below in Scheme 2.

Scheme 2

Synthesis of TFE/HFP from TFE and HFP

[0082] The TFE/HFP compounds in the present refrigerants and/or used in accordance with the present systems and methods have a boiling point of about 72°C, a density of about 1 .54 and a dielectric constant (at 20 GHz of less than 5.4). [0083] The starting materials HFP and TFE or HFIP in preferred embodiments may be present in a stoichiometric ratio of 0.8:1 .2 to 1 .2:0.8. For example, the HFP and TFE may have a stoichiometric ratio of 0.9:1 .1 , 1 .1 :0.9 or 1 :1 .

[0084] The reaction may preferably be carried out in an organic solvent such as dimethylformamide (DMF), acetone, acetonitrile, dimethylsulfoxide (DMSO), and tetrahydrofuran (THF), among others.

[0085] The reaction may preferably be catalyzed by a base such as cesium carbonate (CS2CO3), or other suitable organic or inorganic bases.

[0086] The reaction may preferably be carried out in a reactor that uses a sufficient level of agitation to create a homogenous reaction mixture. Suitable agitation can be achieved by using a mechanical stirrer or magnetic stir bar. The reactor vessel may be coupled to a heating medium to maintain an appropriate reaction temperature. The reactor vessel may be coupled to a cooling bath with any suitable cooling medium to maintain a suitable reaction temperature. The reactor vessel may also be coupled to a condenser with a cooling medium to condense solvent vapors.

[0087] The reaction may 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 encompassed by any two of the foregoing values as endpoints. For example, the reaction may be carried out at a temperature of 10-25°C.

III. Applications of HFPOHFP and TFE/HFP fluoroethers

[0088] A summary of the physical properties of HFPOHFP in the present refrigerants and/or used in accordance with the present systems and methods is provided below in Table 2.

Table 2

[0089] The compositions (including each of Compositions 1A - 1 C) may be used for a variety of applications including but not limited to: (1 ) refrigerants for use in a variety of heat transfer applications (including in thermal management systems and methods); (2) aerosol propellants; (3) blowing agents; (4) gaseous dielectrics; (5) fire suppression agents; (6) solvents; (7) cleaning agents; (8) power cycle working fluids; (9) electrolytes; and (10) starting materials for producing other organofluorine compounds. [0090] The preferred refrigerants of the present invention, including each of Refrigerants 1 through 8, are particularly and unexpectedly advantageous in heat transfer uses and methods, including especially uses and methods relating to the manufacture of electronic components, including preferably semiconductor manufacture. These advantages stem in part from the preferred compositions, including particularly, each of Refrigerants 1 through 7, because of advantageous mosaic of properties possessed by the present refrigerants, including viscosity and/or nonflammability. In particular applications in which electronic components are or may be exposed to the refrigerant, such as in the process of manufacturing electronic components, low dielectric constant is also an important property of the refrigerant.

[0091] The invention includes refrigerants of the present invention, including Refrigerants 1 - Refrigerants 7, in which the refrigerant is non-flammable.

[0092] The invention includes refrigerants of the present invention, including Refrigerants 1 - Refrigerants 7, in which the refrigerant has a dielectric constant less than 3 at 20 GHz.

[0093] The invention includes refrigerants of the present invention, including Refrigerants 1 - Refrigerants 7, in which the refrigerant has a dielectric constant of 2.5 or less at 20 GHz or less.

[0094] The invention includes refrigerants of the present invention, including Refrigerants 1 - Refrigerants 7, in which the refrigerant has a dielectric constant less than 5 at 20 GHz; (ii) has a boiling point of from about 35°C to about 80°C; (iii) is nonflammable; and (iv) has an Ames-negative toxicity. [0095] The invention includes refrigerants of the present invention, including Refrigerants 1 - Refrigerants 7, in which the refrigerant has a boiling point of from about 35°C to about 80°C.

[0096] With particular reference to Figure 1 1 , a side cross-sectional view of a basic refrigerant-cooled wet-etching station is illustrated. The basic operation of such a wet-etching station includes providing a container 15 which holds a bath of chemical etchant 13 for etching a plurality of semiconductor wafers 1 1 . The temperature of the chemical etchant 13 is preferably kept as uniform as possible with the goal of maintaining the surface of wafers 11 such that they are uniformly etched by being immersed in the bath of chemical etchant 13 in container 15. To help maintain such a uniform temperature, a plurality of cooling lines 17 are installed in a portion of the container 15 holding chemical etchant bath 13 such that the cooling lines 17 are in contact with the chemical etchant 13. During wet etching process, the present refrigerants, including particularly each of Refrigerants 1 - 8, circulate through the coolant lines 17 and transport heat from the chemical etchant, either by sensible temperature change, or phase change and/or a combination of sensible temperature change and phase change.

[0097] As mentioned above, the present invention includes methods and uses involving process cooling in, or as part of, electronics component manufacture, including in particular integrated circuit formation (including etching, deposition and the like), and microchip formation (including etching, deposition and the like), using the refrigerants of the present invention, including Refrigerants 1 - Refrigerants 7.

[0098] The table below defines some preferred uses of the present refrigerants, and methods of using the present refrigerants. The first column of Table 3 below identifies and defines the use as Use1 , Use2, etc., and in column 2 one or more of the refrigerants as identified above as Refrigerants 1 - 8 using the abbreviations Ref. 1 , Ref. 2, etc. The designation “NR” is understood to mean that the component or property is not required (but may be present) by the use defined in each particular row of the table.

Table 3

[0099] In other cases, the present refrigerants, including each of Refrigerant 1 through Refrigerant 8, may be used in data centers when excess amounts of heat cannot be controlled by air cooling alone, such as during data tsunamis. In such cases immersion cooling of the electronic component, device and/or article may be required, the present refrigerants, including each of Refrigerant 1 through Refrigerant 8, may be used in such immersion cooling systems which remove heat effectively while maintaining data transfer integrity which is critical, for example, in micro processing devices and battery cooling.

[00100] Exemplary applications of the refrigerants of the present invention, including applications which include immersion cooling, are discussed below.

Heat transfer Applications

[00101] As mentioned above, the present invention provides various methods, processes, and uses of the refrigerants of the present invention, including each of Refrigerants 1 - 8, to transmit heat from one location to another (or from one body, or article or fluid to another body, article or fluid). For example, the refrigerants of the present invention, including each of Refrigerants 1 - 8, may be used to keep the temperature of a component, device and/or article below a defined upper and/or above a defined lower temperature, including especially electronic components, devices and articles. In another example, the present refrigerants, which include refrigerants of the present invention, including each of Refrigerants 1 - 8, may be used for energy conversion, as in the capture of waste heat from industrial or other processes and the conversion to electrical or mechanical energy.

Thermal Management Systems and Methods

[00102] One important category of use of the present refrigerants is in connection with 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 refrigerants of the present invention, including each of Refrigerants 1 - 8, in thermal management systems (hereinafter sometimes referred to as TMS) which operate to maintain an article or device (preferably an electronic component, device, article (including a battery)) or fluid within a certain temperature range, particularly as that article, device or fluid is operating according to its intended purpose and/or during the manufacture of a device or article, particularly during the manufacture an electronic device or component (such as a semiconductor wafer or integrated circuit chip). For example, the TMSs may keep the temperature of a device below a defined upper and/or above a defined lower temperature, including during the processing/manufacture thereof.

[00103] The refrigerants of the present invention, including each of Refrigerant 1 - Refrigerant 8, may be used with a variety of co-refrigerants. Preferred co-refrigerants include hexafluoroisopropylethylether, hexafluoroisopropylmethylthioether, 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).

[00104] Table 4 below defines some preferred refrigerants which are blends comprising HFPOHFP and at least one co-refrigerant. The first column of the table below identifies and defines the Refrigerant Blend by number as RB1 , RB2, etc., and in that column the abbreviations COMP, CEO and CO are used to identify the nature of blend components identified in columns 2 and 3. In particular, the designation COMP in column 1 indicates that the refrigerant comprises HFPOHFP and the indicated corefrigerant. The designation CEO in column 1 means that the refrigerant consists essentially of HFPOHFP and the designated co-refrigerant, and the designation CO in column 1 means that the refrigerant consists of HFPOHFP and the designated co- refrigerant. The second column indicates the amount of HFPOHFP required to be present in the blend. In the third column, the co-refrigerant is identified, and if a specific amount of the co-refrigerant in the blend is required, that is indicated as well.

Table 4 [00105] The invention includes refrigerant blends of the present invention, including each of RB1 - RB20, in which the refrigerant is non-flammable.

[00106] The invention includes refrigerant blends of the present invention, including each of RB1 - RB20, in which the refrigerant has a dielectric constant less than 3 at 20 GHz.

[00107] The invention includes refrigerant blends of the present invention, including each of RB1 - RB20, in which the refrigerant has a dielectric constant less than 2.5 at 20 GHz.

[00108] The invention includes refrigerant blends of the present invention, including each of RB1 - RB20, in which the refrigerant has a dielectric constant less than 5 at 20 GHz; (ii) has a boiling point of from about 35°C to about 80°C; (iii) is nonflammable; and (iv) has an Ames-negative toxicity.

[00109]

[00110] The invention includes refrigerant blends of the present invention, including each of RB1 - RB20, in which the refrigerant has a boiling point of from about 35°C to about 80°C.

[00111] As discussed above, in particular as described in Table 3, the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, can be advantageously used in a method or device or system of cooling and/or heating an electronic device and/or used in a method or device or system for manufacture of an electronic component, device or article (such as a semiconductor wafer or integrated circuit chip).

[00112] Preferred embodiments of the present thermal management methods are now discussed in connection with Figure 1 . An operating electronic device is shown schematically as 10 having a source of electrical energy and/or signals 20 flowing into and/or out of the device 10 and which generates heat as a result of its operation based on the electrical energy and/or signals 20. The refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, are provided in thermal contact with the operating device 10 such that it removes heat, represented by the out flowing arrow 30. Heat is removed from the operating electronic device by sensible heat being added to the liquid thermal management fluid of the present invention (i.e. , increasing the temperature of the liquid), or by causing a phase change in the thermal management liquid (i.e., vaporizing the liquid) or a combination of these. In preferred embodiments, the methods provide a supply of the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, to the device 10 such that the flow of heat from the device 10 through the present refrigerant 30 maintains the operating electrical device at or within a preferred operating temperature range. In preferred embodiments, the preferred operating temperature range of the electrical device is from about 70°C to about 150°C, and even more preferably from about 70°C to about 120°C, and the flow of heat 30 from the device 10 through the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, maintains the operating electrical device at or within such preferred temperature ranges. Preferably, the refrigerant 30 of the present invention, which has absorbed heat from the device, is in thermal contact with a heat sink, represented schematically as 40, at a temperature below the temperature of the heat transfer fluid 30 and thereby transfers the heat generated by the device 10 to the heat sink 40. In this way, the heat-depleted refrigerant 50 can be returned to the electronic device 10 to repeat the cycle of cooling. [00113] In a preferred embodiment of the present methods, the step of removing heat through the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, comprises evaporating the refrigerant using the heat generated by the operation of the electronic device, and the step of transferring that heat from the refrigerant to the heat sink comprises condensing the refrigerant by rejecting heat to the heat sink. In such methods, the temperature of the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, during said evaporation step is preferably greater than 50°C, or preferably greater than about 55°C, or preferably in the range of from about 55°C to about 85°C, or preferably from about 65°C to about 75°C. Applicants have found that the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, provide excellent performance in such methods and at the same time allow the use of relatively low cost, lightweight and reliable equipment to provide the necessary cooling, as will be explained further in connection with particular embodiments as described in connection with Figure 2A below. [00114] In a further preferred embodiment of the present methods, the step of removing heat through the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, comprises adding sensible heat to the refrigerant (e.g., raising the temperature of the liquid up to about 70°C or less at about atmospheric pressure, i.e., wherein the fluid is not required to be in a high pressure container or vessel) using the heat generated by the operation of the electronic device, and the step of transferring that heat from the refrigerant to a heat sink and thereby reducing the liquid temperature by rejecting heat to the heat sink. The cooled liquid is then returned to thermal contact with the electrical device wherein the cycle starts over. In preferred embodiments, the temperature of the refrigerant that transfers heat to the heat sink is greater than about 40°C, or preferably greater than about 55°C, or preferably in the range of from about 45°C to about 70°C, or preferably from about 45°C to about 65°C, and preferably is at a pressure that is about atmospheric. Applicants have found that the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, provide excellent performance in such methods and at the same time allow the use for relatively low cost, lightweight and reliable equipment to provide the necessary cooling, as will be explained further in connection with particular embodiments as described in connection with Figure 2B below.

[00115] It will be appreciated by those skilled in the art that the present invention comprises systems and methods which use both sensible heat transfer and phase change heat transfer as described above.

[00116] A particular method according to the present invention will now be described in connection with Figures 2A and 2B in which an electronic device 10 is contained in an appropriate container 12, and preferably a sealed container, and is in direct contact with, and preferably fully immersed in liquid the refrigerants 11 A (shown schematically by gray shading) of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20. For the purposes of convenience, such cooling methods, devices and system are sometimes referred to herein as “immersion cooling” methods, devices and systems.

[00117] In immersion cooling methods, devices and systems used to cool electrical devices or components, the operating electronic device 10 has a source of electrical energy and/or signals 20 flowing into and/or out of the container 12 and into and/or out of device 10, which generates heat as a result of its operation based on the electrical energy and/or signals 20. As those skilled in the art will appreciate, it is a significant challenge to discover a refrigerant that can perform effectively in such applications since the fluid must not only provide all of the other properties mentioned above, but it must also be able to do so while in intimate contact with an operating electronic device, that is, one which involves the flow of electrical current/signals. It will be appreciated that many fluids that might be otherwise viable for use in such applications will not be useable because they will either short-out the device, degrade when exposed to the conditions created by the operation of the electronic device (i.e., degrade the cooling effect over time and/or the operating stability of the device), or have some other property detrimental to operation when in contact with an operating electronic device.

[00118] In contrast, the present thermal management methods produce excellent and unexpected results by providing the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, in direct thermal and physical contact with the device 10 as it is operating. This heat of operation is safely and effectively transferred to the refrigerant 11 A by: (a) causing the liquid phase of the fluid refrigerant to evaporate and form vapor 11 B; or (b) raising the temperature of the liquid refrigerant 1 1 A; or (c) a combination of (a) and (b).

[00119] When the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is a single-phase liquid, it will remain liquid when heated by the heat-generating component. Thus, the refrigerant can be brought into contact with the heat generating component, resulting in the removal of the heat from the heat generating component and the production of a refrigerant with a higher temperature. The refrigerant is then transported to a secondary cooling loop, such as a radiator or another refrigerated system. An example of such a system is illustrated in Figure 2, where the refrigerant enters a battery pack enclosure containing a number of cells and exits the enclosure having taken up heat from the battery pack.

[00120] When the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is present in two phases, the heat-generating component is in thermal contact with the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, and transfers heat to the refrigerant, resulting in the boiling thereof. The refrigerant is then condensed. An example of such a system is where the heat-generating component is immersed in the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, and an external cooling circuit condenses the boiling fluid into a liquid state.

[00121] In the case of the phase change heat transfer systems of the present invention, reference is made herein to Figure 2A. In such an operation, heat is carried away from device 10 as the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, evaporates and the vapor rises through the remaining refrigerant liquid in the container 12. The refrigerant vapor 11 B then rejects the heat it has absorbed to a heat sink 40, which can be an enclosed heat sink 40A and/or an external heat sink 40B. An example of a heat sink that is internal to the container 12 are condenser coils 30A and 30B with circulating liquid, such as water, at a temperature below the condensing temperature of the refrigerant vapor. An example of a heat sink that is external to the container 12 would be passing relatively cool ambient air over the container 12 (which preferably in such case include cooling fins or the like), which will serve to condense the heat transfer vapor 11 B on the interior surface of the container. As a result of this condensation, liquid refrigerant is returned to the pool of liquid fluid 11 A in which device 10 remains immersed in operation.

[00122] In the case of a sensible heat transfer systems of the present invention, reference is made herein to Figure 2B. In such an operation heat is carried away from the device as the temperature of liquid 11 A, including the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, increases upon accepting heat being generated by the device, which is immersed, and preferably substantially fully immersed in the refrigerant 11 A of the present invention. The higher temperature refrigerant liquid 1 1 A then rejects the heat it has absorbed to a heat sink 40, which can be an enclosed heat sink 40A and/or an external heat sink 40B. An example of a heat sink that is internal to the container 12 are cooling coils 30A and 30B with circulating liquid, such as water, at a temperature below the temperature of heated liquid. An example of a heat sink that is external to the container 12 would be removing heated liquid 11 A from the container through a conduit 45 where it is thermally contacted with a cool fluid, such as might be provided by relatively cool ambient air, or cooled water or refrigerant, which will serve to lower the temperature of the liquid. Cooled liquid is then returned via conduit 46.

[00123] Optionally, but preferably in certain embodiments involving thermal management of the batteries used in electronic vehicles, the thermal management system includes a heating element which is able to heat the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, such as for example an electrical heating element 60 which is also immersed in the refrigerant. As those skilled in the art will appreciate, the batteries in electronic vehicles (which would correspond to the operating electronic device 10 in Figures 2A and 2B) can reach relatively low temperatures while parked outside in the winter months in many geographical locations, and frequently such low temperature conditions are not desirable for battery operation. Accordingly, the thermal management system of the present invention can include sensors and control modules (not shown) which turn on the heating element when the battery temperature is below a predetermined level. In such a case, the heater 60 would be activated, the refrigerant liquid 11 A would be heated, and would in turn transfer this heat 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 - 8 and RB1 - RB20, would serve the cooling function as described above.

[00124] For the purposes of this invention, the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, can be in direct contact with the heat-generating component or in indirect contact with the heat-generating component.

[00125] When the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is in indirect contact with the heat-generating component, the refrigerant fluid can be used in a closed system in the electronic device, which may include at least two heat exchangers. When the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, are used to cool the heat-generating component, heat can be transferred from the component to the refrigerant, usually through a heat exchanger in contact with at least a part of the component or the heat can be transferred to circulating air which can conduct the heat to a heat exchanger that is in thermal contact with the refrigerant.

[00126] In a particularly preferred feature of the present invention, the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is in direct contact with the heat-generating component. In particular, the heat generating component is fully or partially immersed in the refrigerant. Preferably the heat generating component is fully immersed in the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20. The refrigerant, as a warmed fluid or as a vapor, can then be circulated to a heat exchanger which takes the heat from the fluid or vapor and transfers it to the outside environment by way of a heat sink such as ambient air or water cooled by ambient air or otherwise. After this heat transfer, the cooled refrigerant (cooled or condensed) is recycled back into the system to cool the heat-generating component.

[00127] Electrical conductivity and/or dielectric strength of a refrigerant becomes important if the fluid comes in direct contact with the electronic components of the electronic device (such as in direct immersion cooling), or if the refrigerant leaks out of a cooling loop or is spilled during maintenance and comes in contact with the electrical circuits. Thus, the refrigerants of the present invention, including each of Refrigerants 1

- 8 and RB1 - RB20, is preferably an electrically insulating thermal management fluid. [00128] The refrigerants of the present invention, including each of Refrigerants 1

- 8 and RB1 - RB20, may be recirculated passively or actively in the device, for example by using mechanical equipment such as a pump. In a preferred feature of the present invention, the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is recirculated passively in the device.

[00129] Passive recirculating systems work by transferring heat from the heatgenerating component to the refrigerant until it typically is vaporized, allowing the heated vapor to proceed to a heat exchange surface at which it transfers its heat to the heat exchanger surface and condenses back into a liquid. It will be appreciated 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. The condensed liquid then returns, preferably fully passively by the force of gravity and/or a wicking structure, into the refrigerant in contact with the heat-generating component. Thus, in a preferred feature of the invention, the step of transferring heat from the heat-generating component to the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, causes the thermal management fluid to vaporize.

[00130] Examples of passive recirculating systems include a heat pipe or a thermosyphon. Such systems passively recirculate the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, using gravity. In such a system, the refrigerant is heated by the heat-generating component, resulting in a heated refrigerant which is less dense and more buoyant. This refrigerant travels to a storage container, such as a tank where it cools and condenses. The cooled refrigerant then flows back to the heat source.

Electrical Device Cooling

[00131] The present disclosure includes the use of the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, to cool and optionally heat electronic devices that produce or include a component that is 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 this invention, the heat generating component includes but is not limited to: semiconductor integrated circuits (ICs), electrochemical cells, power transistors, resistors, and electroluminescent elements, such as microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, electrical distribution switch gear, power transformers, circuit boards, 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, e.g. used for high power applications such as, for example, hybrid or electric vehicles. [00132] For the purpose of this invention, the electronic device includes but is not limited to: personal computers, microprocessors, servers, cell phones, tablets, digital home appliances (e.g., televisions, media players, games consoles etc.), personal digital assistants, datacenters, batteries both stationary and in vehicles, including Li-ion batteries and other batteries used in hybrid or electric vehicles, wind turbine, train engine, or generator. Preferably the electronic device is a hybrid or electric vehicle. [00133] The present invention further relates to an electronic device comprising a the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20. For the purposes of this invention, the refrigerant is provided for cooling and/or heating the electronic device.

[00134] The present invention further relates to an electronic device comprising a heat generating component and a refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, for cooling, and optionally heating, the electronic device.

[00135] The present invention further relates to an electronic device comprising a heat generating component, a heat exchanger, a pump and a refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20. For the purpose of this invention, the electronic device can be any such device, including but not limited to personal computers, microprocessors, servers, cell phones, tablets, digital home appliances (e.g. televisions, media players, games consoles etc.), personal digital assistants, datacenters, hybrid or electric vehicles, batteries both stationary and in vehicles, electrical drive motors, fuel cells (e.g., hydrogen fuel cells) and electrical generators, preferably wherein the electronic device is in a hybrid vehicle, or electric vehicle, or wind turbine, or train.

[00136] For the purposes of this invention, the heat generating component can be any electrical component that generates heat during operation and/or during the manufacture thereof, including electronic components that generate and/or are exposed to heat at high levels of heat flux. Examples components that can be cooled during operatation and/or manufacture using the refrigerants of the present invention, including Refrigerant 1 - Refrigerant 8 and RB1 - RB20, include semiconductor integrated circuits (ICs), electrochemical cells, power transistors, resistors, and electroluminescent elements, such as microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, electrical distribution switch gear, 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, e.g. used for high power applications such as, for example, hybrid or electric vehicles.

Lithium-Ion Battery Cooling Systems

[00137] Examples of the present thermal management methods useful for lithium- ion battery cooling, including the use of refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, in such methods, including Heat Transfer Method 1 , will now be described in connection with Figure 8. A vehicle battery pack with a self-contained liquid cooling system 10 comprising a module 12 formed of a container 14 with an interior space 16 for supporting a battery assembly 18. Container 14 is a closed and sealed container 14 for forming a 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 is Li-ion batteries for use in a Battery Electric Vehicle (BEV). Additional batteries for use with other prime mover vehicles may be provided with the liquid cooling system 10 of the present invention, where each battery cell includes active material for generating power from an electrochemical reaction within the interior space 16 of the container 14. The battery cells 20 are preferably stacked to form a battery cell stack 22. In the embodiment shown, a gap 24 between each battery cell 20 is between 0.25-0.50 mm, forming a fluid channel 26 between each battery cell 20. In another embodiment, the gap 24 may be less than 0.25 mm. It is understood that other gap sizes can be used as desired.

[00138] A composition of the present invention, including Compositions 1 , and the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is disposed within the interior space 16 of the container 14 and the fluid level shown is such that the battery assembly 18 is completely immersed within the composition/refrigerant of the present invention. The composition of the present invention, including Composition 1 , and the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is in contact with the battery cells 20 through the fluid channels 26 formed by gaps 24. [00139] A heating element 34 is located at a base area 36 of the container 14. The heating element 34 shown is an electronic heating element. It is understood that other heating element types may be used. The heating element 34 is shown as a single element; however, multiple heating elements 34 such as heating plates may be provided.

[00140] A cooling element 38 is located at an upper area 40 of the container 14. The cooling element 38 may be a chilled water condenser having an inlet 42 and an outlet 44 extending beyond the walls of the sealed container 14 for importing and exporting water for the cooling element 38. In another embodiment, the cooling element 38 may be a chilled water plate. In still another embodiment, the cooling element 38 may be a thin aluminum heat sink having external chilled water travelling through the cooling element 38. The cooling element 38 may be a graphite foil impregnated with an electrically nonconductive polymer. The cooling element may also be formed from copper.

[00141] In the embodiment shown, arrows “A” and “B” indicate a flow 28 of the composition of the present invention, including Composition 1 , and the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20. Upon heating of each battery cell 20 by the heating element 34, the fluid 28, including compositions of the present invention, including Compositions 1 , and the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is exposed to a front surface area 30 and a rear surface area 32 of the battery cells 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 return to the base area 36, generally following either coolant paths “A” or “B.” Where the general location of the coolant 28 at the moment of boiling is located within the fluid channels 26 of the battery cells 20 in the center area and toward a side 50 of the container 14, the coolant 28 will tend to follow flow path “A”. Similarly, if the general location of the dielectric coolant 28 at the moment of boiling is located within the fluid channels 26 of the battery cells 20 in the center area and toward an opposing side 52 of the container 14, the dielectric coolant 28 will tend to follow flow path “B”. [00142] A coolant temperature sensor 46 is located on or near the cooling element 38. In the embodiment shown, the temperature sensor 46 is located within the area of the outlet 44 of the cooling element 38 and measures a temperature of the dielectric coolant 28 of the present invention at a point of exposure to the cooling element. The temperature sensor 46 may be located anywhere within the battery cell stack 22 as desired.

[00143] A coolant level sensor 48 is also provided and is located near the upper area 40 of the container 14 to measure the fluid level of the dielectric coolant 28, including compositions of the present invention, including Composition 1 , and the refrigerants of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, within the container 14, ensuring complete immersion of the battery assembly 18 within the dielectric coolant 28.

Heat Pipe Cooling and Heating

[00144] An example of the present heat transfer methods using a heat pipe is now described with respect to Figure 10, which is a specific example of a heat pipe in an energy storage assembly 1 according to one exemplary embodiment of the invention. The energy storage assembly 1 may be part of a motor vehicle 12, in particular of a hybrid or electric vehicle, and is provided to supply electric power to electric consumers, like e.g., an electrical drive unit (not shown), on the motor vehicle side. The energy storage assembly 1 includes a plurality of electrical energy stores. 2. The electrical energy stores 2 are electrically connected via an electric connection element (not shown), in particular in the form of a conductive rail or conductor rail (“bus bar”), i.e. , connected in series or in parallel. The electric connection element contacts hereby corresponding electrical connectors (not shown) arranged on respective exposed outer wall sections of corresponding energy storage housings (not shown) of the energy stores 2 in parallel alignment arranged adjacent to one another to thereby form an energy store stack (“stack”). Plate-shaped spacer elements 3 are respectively arranged between the energy stores 2 to separate them and at the same time thermally conductive properties. The spacer elements 3 thus provide, on one hand, spacing between immediately adjacent energy stores 2 so that immediately adjacent energy stores 2 do not contact each other electrically or mechanically. On the other hand, the spacer elements 3 act as a result of their thermally conductive properties as heat conductors for the purpose of cooling the energy stores 2 or the energy storage assembly 1 by dissipating heat, particularly from the contacting energy stores 2, or, for the purpose of heating the energy stores 2 or energy storage assembly 1 by supplying heat, particularly to the contacting energy stores 2. A heat pipe 4 of a first heat pipe assembly 5 and of a heat pipe 6 of a second heat pipe assembly 7 are provide. The heat pipes 4, 6 thus extend along this side surface of the energy store stack and are thermally coupled to the spacer elements 3, respectively. The spacer elements 3 thus form a thermal bridge between the heat pipes 4 of the first heat pipe assembly 5 and the heat pipes 6 of the second heat pipe assembly 7, on one hand, and the energy stores 2, on the other hand. The respective heat pipes 4 of the first heat pipe assembly 5 are arranged and aligned such as to be thermally coupled with respective evaporation zones, in which a contained refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, can be evaporated, to the spacer elements 3. Heat (evaporation heat) required for the evaporation of the present refrigerant is thus removed from the spacer elements 3 or via the spacer elements 3 from the energy stores 2. The energy stores 2, including the energy storage assembly 1 , can thus be cooled via the heat pipes 4 of the first heat pipe assembly 5. Also, the respective condensation zones of the heat pipes 4 of the first heat pipe assembly 5, in which condensation zones a contained gaseous refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, can be condensed, are thermally coupled with a heat sink 8 in the form of a motor-vehicle-side heat exchanger. Heat (condensation heat) generated during condensation of the present refrigerant can thus be transferred to the heat sink 8. The heat exchanger can be part of the energy storage assembly 1 , i.e., belong to or associated with the energy storage assembly 1 . The respective heat pipes 6 of the second heat pipe assembly 7 are arranged and aligned such as to be thermally coupled with their respective condensation zones, in which the contained gaseous refrigerant of the present invention can be condensed, to the spacer elements 3. Heat (condensation heat) can thus be transferred during condensation of the present refrigerant to the spacer elements 3 or via the spacer elements 3 to the energy stores 2. Thus, the energy stores 2 and the energy storage assembly 1 , can be heated via the heat pipes 6 of the second heat pipe assembly 7. Also, the respective evaporation zones of the heat pipes 6 of the second heat pipe assembly 7, in which evaporation zones a contained refrigerant of the present invention can be evaporated, are thermally coupled with a heat source 9 in the form of a functional component, i.e., e.g., a charger or a control device or a control electronics, associated to the energy storage assembly 1 . 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 implementation of a temperature control device for controlling the temperature, i.e., for heating or cooling, of the energy stores 2 of the energy storage assembly 1 . The heat pipes useful according to the present invention include both gravity return heat pipe, capillary return heat pipe and gravity/capillary return heat pipes.

Organic Rankine Cycles

[00145] When a refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is used in an Organic Rankine cycle, it may be referred to as a working fluid.

[00146] The working fluid therefore corresponds to refrigerant as discussed in this application. All preferred features of the heat transfer fluid apply to the working fluid as described herein.

[00147] Rankine cycle systems are known to be a simple and reliable means to convert heat energy into mechanical energy in the form of shaft power. In industrial settings, it may be possible to use flammable working fluids such as toluene and pentane, particularly when the industrial setting has large quantities of flammables already on site in processes or storage. However, for instances where the risk associated with use of a flammable and/or toxic working fluid is not acceptable, such as power generation in populous areas or near buildings, it is necessary or at least highly desirable to use non-flammable and/or non-toxic refrigerants as the working fluid. There is also a drive in the industry for these materials to be environmentally acceptable in terms of GWP.

[00148] The process for recovering waste heat in an Organic Rankine cycle according to the present invention preferably involves pumping liquid-phase working fluids of the present invention, including the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, through a boiler where an external (waste) heat source, such as a process stream, heats the working fluid causing it to evaporate into a saturated or superheated vapor. This vapor is expanded through a turbine wherein the waste heat energy is converted into mechanical energy.

Subsequently, the vapor phase working fluid is condensed to a liquid and pumped back to the boiler in order to repeat the heat extraction cycle.

[00149] Referring to Figure 4, in an exemplary organic Rankine cycle system 70, working fluid of the present invention, including refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, is circulated between an evaporator 71 and a condenser 75, with a pump 72 and an expansion device 74 functionally disposed therebetween. In the illustrated embodiment, an external flow of fluid is directed to evaporator 71 via external warm conduit 76. External warm conduit 76 may carry fluid from a warm heat source, such as a waste heat source from industrial processes (e.g., power generation), flue gases, exhaust gases, geothermal sources, etc.

[00150] Evaporator 71 is preferably configured as a heat exchanger which may include, e.g., a series of thermally connected, but fluidly isolated, tubes carrying fluid from warm conduit 76 and fluid from working fluid conduit 77B respectively. Thus, evaporator 71 facilitates the transfer of heat QIN from the warm fluid arriving from external warm conduit 76 to the relatively cooler (e.g., “cold”) working fluid arriving from expansion device 74 via working fluid conduit 77B.

[00151] The working fluid of the present invention, including the present fluoroethers, thus exits from evaporator 71 , having been warmed by the absorption of heat QIN, and then travels through working fluid conduit 78A to pump 72. Pump 72 pressurizes the working fluid, thereby further warming the fluid through external energy inputs (e.g., electricity). The resulting “hot” fluid passes to an input of condenser 75 via conduit 78B, optionally via a regenerator 73 as described below.

[00152] Condenser 75 is configured as a heat exchanger similar to evaporator 71 , and may include, e.g., a series of thermally connected, but fluidly isolated, tubes carrying fluid from cool conduit 79 and fluid from working fluid conduit 78B respectively. Condenser 75 facilitates the transfer of heat QOUT to the cool fluid arriving from external cool conduit 79 to the relatively warmer (e.g., “hot”) working fluid of the present invention, including the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, arriving from pump 72 via working fluid conduit 78B.

[00153] The working fluid of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, exiting from condenser 75, having thus been cooled by the loss of heat QOUT, then travels through working fluid conduit 77A to expansion device 74. 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 present fluoroethers, may perform work, e.g., by driving a turbine. The resulting “cold” fluid passes to an input of evaporator 71 via conduit 77B, optionally via a regenerator 73 as described below, and the cycle begins anew.

[00154] Thus, working fluid conduits 77A, 77B, 78A and 78B define a closed loop such that the working fluid contained therein may be reused indefinitely, or until routing maintenance is required.

[00155] In the illustrated embodiment, regenerator 73 may be functionally disposed between evaporator 71 and condenser 75. Regenerator 73 allows the “hot” working fluid of the present invention, including the present fluoroethers, exiting from pump 72 and the “cold” working fluid issued from expansion device 74 to exchange some heat, potentially with a time lag between deposit of heat from the hot working fluid and release of that heat to the cold working fluid. In some applications, this can increase the overall thermal efficiency of Rankine cycle system 70.

[00156] The invention also provides a process for converting thermal energy to mechanical energy in a Rankine cycle, the method comprising the steps of i) vaporizing a working fluid of the invention, including refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, with a heat source and expanding the resulting vapor, then ii) cooling the working fluid with a heat sink to condense the vapor, wherein the working fluid is a refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20.

[00157] The mechanical work may be transmitted to an electrical device such as a generator to produce electrical power.

[00158] The heat source maybe provided by, for example, a thermal energy source selected from industrial waste heat, solar energy, geothermal hot water, low pressure steam, distributed power generation equipment utilizing fuel cells, prime movers, or an internal combustion engine. The low-pressure steam is preferably a low- pressure geothermal steam or is provided by a fossil fuel powered electrical generating power plant.

[00159] The heat source is preferably provided by a thermal energy source selected from industrial waste heat, or an internal combustion engine.

[00160] It will be appreciated that the heat source temperatures can vary widely, for example from about 90^QC to >800^sC, and can be dependent upon a myriad of factors including geography, time of year, etc. for certain combustion gases and some fuel cells.

[00161] Systems based on sources such as waste water or low pressure steam from, e.g., a plastics manufacturing plants and/or from chemical or other industrial plant, petroleum refinery, and related word forms, as well as geothermal sources, may have source temperatures that are at or below about 175 ^QC or at or below about 100°C, and in some cases as low as about 90°C or even as low as about 80°C. Gaseous sources of heat such as exhaust gas from combustion process or from any heat source where subsequent treatments to remove particulates and/or corrosive species result in low temperatures may also have source temperatures that are at or below 200°C, at or below about 175°C, at or below about 130°C, at or below about 120°C, at or below about 100°C, at or below about 100°C, and in some cases as low as about 90°C or even as low as about 80°C.

[00162] However, it is preferred in some applications that the heat source has a temperature of at least about 200°C, for example of from about 200°C to about 400°C. [00163] In an alternative preferred embodiment, the heat source has a temperature of from 400^QC to 800^QC, more preferably 400^QC to 600^QC.

Heat Pumps

[00164] The refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, may be used in a high temperature heat pump system.

[00165] Referring to Figure 5, in one exemplary heat pump system, compressor 80, such as a rotary, piston, screw, or scroll compressor, compresses a refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, which is conveyed to a condenser 82 to release heat QOUT to a first location, followed by passing the refrigerant through an expansion device 84 to lower the refrigerant pressure, followed by passing the refrigerant through an evaporator 86 to absorb heat QIN from a second location. The refrigerant is then conveyed back to the compressor 80 for compression.

[00166] The present invention provides a method of heating a fluid or body using a high temperature heat pump, said method comprising the steps of (a) condensing a refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, in the vicinity of the fluid of body or be heated, and (b) evaporating said refrigerant.

[00167] Examples of high temperature heat pumps include a heat pump tumble dryer or an industrial heat pump. It will be appreciated that the heat pump may comprise a suction line/liquid line heat exchanger (SL-LL HX). By “high temperature heat pump”, it is meant a heat pump that is able to generate temperatures 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.

Secondary Loop System

[00168] The refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, may be used as secondary refrigerant fluid in a secondary loop system.

[00169] A secondary loop system contains a primary vapor compression system loop that uses a primary refrigerant and whose evaporator cools the secondary loop fluid. The secondary refrigerant fluid, including refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, then provides the necessary cooling for an application. The secondary refrigerant fluid should preferably be nonflammable and have low toxicity since the fluid in such a loop is potentially exposed to humans in the vicinity of the cooled space. In other words, the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, may be used as a “secondary refrigerant fluid” in a secondary loop system.

[00170] Referring to Figure 6, one exemplary secondary loop system includes a primary loop 90 and a secondary loop 92. In primary loop 90, compressor 94, such as a rotary, piston, screw, or scroll compressor, compresses a primary refrigerant, which is conveyed to a condenser 96 to release heat QOUT to a first location, followed by passing the primary refrigerant through an expansion device 98 to lower the refrigerant pressure, followed by passing the primary refrigerant through a refrigerant/secondary fluid heat exchanger 100 to exchange heat QIN with a secondary fluid, including the present fluoroethers, with the secondary fluid pumped through secondary loop 92 via a pump 102 to a secondary loop heat exchanger 104 to exchange heat with a further location, for example to absorb heat QIN-S to providing cooling to the further location. [00171] The primary fluid used in the primary loop (vapor compression cycle, external/outdoors part of the loop) may 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.

[00172] The secondary loop system may be used in refrigeration or air conditioning applications, that is, the secondary loop system may be a secondary loop refrigeration system or a secondary loop air conditioning system.

[00173] Examples of refrigeration systems which can include a secondary loop refrigeration system that include a secondary refrigerant of the present invention, including the present fluoroethers, include: a low temperature refrigeration system, a medium temperature refrigeration system, a commercial refrigerator, a commercial freezer, an industrial freezer, an industrial refrigerator, and a chiller.

[00174] Examples of air conditioning systems which can include a secondary loop air conditioning system which utilize a refrigerant of the present invention, including the present fluoroethers, include in mobile air conditioning systems or stationary air conditioning systems. Mobile air-conditioning systems including air conditioning of road vehicles such as automobiles, trucks and buses, as well as air conditioning of boats, and trains. For example, where a vehicle contains a battery or electric power source. [00175] Examples of stationary air conditioning systems which can include a secondary loop air conditioning system which utilize a refrigerant of the present invention, including the present fluoroethers, include: a chiller, particularly a positive displacement chiller, more particularly an air cooled or water-cooled direct expansion chiller, which is either modular or conventionally singularly packaged, a residential air conditioning system, particularly a ducted split or a ductless split air conditioning system, a residential heat pump, a residential air to water heat pump/hydronic system, an industrial air conditioning system, a commercial air conditioning system, particularly a packaged rooftop unit and a variable refrigerant flow (VRF) system, and a commercial air source, water source or ground source heat pump system.

[00176] A particularly preferred heat transfer system according to the present invention is an automotive air conditioning system comprising a vapor compression system (the primary loop) and a secondary loop air conditioning system, wherein the primary loop contains HFO-1234yf as the refrigerant and the second loop contains a refrigerant or heat transfer composition of the present invention, including the present fluoroethers. In particular, the secondary loop can be used to cool a component in the car engine, such as the battery.

[00177] It will be appreciated the secondary loop air conditioning or refrigeration system may comprise a suction line/liquid line heat exchanger (SL-LL HX).

[00178] The present heat transfer fluids, or heat transfer compositions which can include a secondary loop air conditioning system which utilize a refrigerant of the present invention, including the present fluoroethers, may be used as a replacement for existing fluids.

[00179] The invention includes a method of replacing an existing heat transfer fluid in a heat transfer system, said method comprising the steps of (a) removing at least a portion of said existing heat transfer fluid from said system, and subsequently (b) introducing into said system a heat transfer fluid of the invention. 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 said existing heat transfer fluid from said system prior to step (b).

[00180] The method may optionally comprise the step of flushing said system with a solvent after conducting step (a) and prior to conducting step (b).

[00181] For the purposes of this invention, the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, can be used to replace an existing fluid in an electronic device, in an Organic Rankine cycle, in a high temperature heat pump or in a secondary loop.

[00182] For example, the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, may be used as a replacement for existing fluids such as HFC-4310mee, HFE-7100 and HFE-7200. Alternatively, the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, can be used to replace water and glycol. The replacement may be in existing systems, or in new systems which are designed to work with an existing fluid. Alternatively, the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, can be used in applications in which the existing refrigerant was previously used. Alternatively, the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, may be used to retrofit an existing refrigerant in an existing system.

Alternatively, the refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20, may be used in new systems which are designed to work with an existing refrigerant.

[00183] The invention provides a method of replacing an existing refrigerant in a heat transfer system, said method comprising the steps of (a) removing at least a portion of said existing refrigerant from said system, and subsequently (b) introducing into said system refrigerant of the present invention, including each of Refrigerants 1 - 8 and RB1 - RB20. The existing refrigerants may be selected, for example, from HFC- 4310mee, HFE-7100 and HFE-7200.

[00184] 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 said existing refrigerant from said system prior to step (b).

[00185] The method may optionally comprise the step of flushing said system with a solvent after conducting step (a) and prior to conducting step (b).

Solvent and Cleaning Uses, Methods, and Systems [00186] The present invention provides solvating methods. Such methods include cleaning methods generally, etching methods, carrier solvent applications (for coating applications, lubricant deposition, silicone deposition, and other coatings, including in connection with coatings of medical devices heparin and PTFE for example) using a composition of the present invention, including Composition 1.

[00187] With respect to cleaning methods, all such methods are included within the scope of the present invention. Preferred cleaning methods include vapor degreasing by contacting the article, device or component thereof with a composition of the present invention, including Composition 1 . A wide variety of contaminants can be removed from a wide variety of articles, devices and components. Examples of contaminants that can be removed using a composition of the present invention, including the present fluoroethers, include, for example, light oils, medium oils, fluorolubes, greases and silicones and waxes. Examples of article, device and components that can be cleaned using a composition of the present invention, including Composition 1 , include, for example electronic components (including silicon wafers, PCBs, semiconductor surfaces), precision parts (including aircraft parts and components) light oils, medium oils, fluorolubes, greases and silicones and waxes.

[00188] Preferred solvent vapor phase degreasing and defluxing methods of the present invention include immersing a soiled substrate or part (e.g., a printed circuit board or a fabricated metal, glass, ceramic, plastic, or elastomer part or composite) or a portion of a substrate or part into a boiling, non-flammable liquid in accordance with the present invention, including a composition of the present invention, including Composition 1 , followed by rinsing the part in a second tank or cleaning zone by immersion or distillate spray with a clean solvent which can also be any one of the compositions of the present invention. The parts are then dried by maintaining the cooled part in the condensing vapors until temperature has reached equilibrium.

[00189] Solvent cleaning of various types of parts generally occurs in batch, hoist- assisted batch, conveyor batch, or in-line type conveyor degreaser and defluxer equipment. Parts may also be cleaned in open top defluxing or degreasing equipment. In both types of equipment, the entrance and/or exit ends of the equipment can be in open communication with both the ambient environment and the solvent within the equipment. In order to minimize the loss of solvent from the equipment by either convection or diffusion, a common practice in the art is to use.

[00190] The present invention includes solvent compositions comprising a composition of the present invention, including Composition 1 , in combination with a cosolvent. The co-solvent may be selected from the group consisting of hexafluoroisopropylethylether, hexafluoroisopropylmethylthioether, 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).

Electrolyte Formulations and Batteries

[00191] The present invention also provides electrolyte formulations, and batteries containing electrolyte formulations, which comprise a composition of the present invention, including Composition 1 . In general, the electrolyte formulations comprise: (a) electrolyte; (b) organic solvent for the electrolyte; and (c) additives that are included in the formulation to provide a desired property, or an improvement to a desired property, of the electrolyte formulation and/or of the battery which contains the electrolyte. A 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.

[00192] Thus, the present invention provides electrolyte formulations comprising: a salt, preferably lithium-ion salt; a solvent for the salt, said solvent comprising a composition of the present invention, including Composition 1 either with or without a co-solvent; and one or more additives different than the compounds of the present invention. The present invention also provides electrolyte formulations comprising: electrolyte, and preferably lithium ion electrolyte; (b) solvent for the lithium-ion electrolyte; and (c) an additive comprising a composition of the present invention, including Composition 1 , either with or without additional additives.

[00193] The present invention also provides batteries in general, and rechargeable lithium-ion batteries in particular, which contain an electrolyte formulation containing a composition of the present invention, including Composition 1. An exemplary rechargeable lithium-ion battery is illustrated in Figure 9 hereof, which shows a cathode and an anode and electrolyte formulation of the present invention which facilitates the flow of lithium ions between the cathode and the anode.

[00194] Although it is contemplated that the present electrolyte formulations may be useful in batteries in general, in preferred embodiments the electrolyte formulation comprises a lithium-ion electrolyte useful in rechargeable batteries. Non-limiting examples of lithium salts that may comprise the electrolyte portion of the formulation include: LiPF₆, LiAsF₆, LiCIO₄*LiBF₄, LiBC₄Og(LiBOB), LiBCO₄F,(LiODFB),LiPF₃ (C₂F₅)3(LiFAP), LiBF3(C2F₅)LiPF3(C,F₅)3(LiFAB), LiN, (CF₃SO,) LiN(C,F₅SO,), LiCF₃S03,LiC(CF₃SO)3, LiPF₄(CF₃)2,LiPF3(CF₃)3, LiPF₃(iSO-C₃C7)3, LiPF₅(iso-C₃F7). The overall salt concentration may vary depending on the particular needs of the application, in some embodiments the electrolyte may be present in the formulation in an amount between about 0.3M and about 2.5M or, from about 0.7M to about 1 .5M.

EXAMPLES

Example 1 - Synthesis of HFPOHFP from HFP and HFIP

[00195] HFPOHFP was synthesized from HFP and HFIP according to the following procedure.

[00196] 250 mL of DMF and 10 g of cesium carbonate were charged into a 3 necked 500 mL round bottom jacketed flask equipped with a mechanical stirrer, a dry ice condenser, a gas sparger (for HFP) and a temperature sensor. The condenser outlet was attached to a nitrogen tee. Cooling water was turned on before 125 mL of HFIP was added. At this point, a slight exotherm was observed. The reaction was allowed to cool to less than 25°C. Next, 200 g of HFP was added over a period of 60 minutes using a sparger and a needle valve such that the temperature of the reaction mixture did not exceed 25°C. The reaction was observed to be exothermic and turned a slight yellow color towards the end of the addition. Once the reaction was almost finished, the exotherm slowed and the temperature of the reaction dropped quickly. The reaction mixture from the flask was decanted and filtered, then rotovapped at 45°C and 60-70 torr. The reboiler heavies were poured into water and the lower layer (a colorless liquid) was separated to afford 325.0 g, (81 % yield, GC 83.39%). Alternately, the reaction mixture was decanted, and fully rotovapped under the same conditions to afford 323.8g, (80.6% yield, GC 82.92%). The material was then distilled and combined to give a total of 562.8 g of material over 95% by GC.

[00197] The reagents used and their physical properties, together with the molecular weight, boiling point and density of the HFPOHFP produced are shown below in Table E1 A.

Table E1 A [00198] The HFPOHFP was also tested to determine its density over a range of temperatures using Ubbelohde tube in accordance with the procedure described in ASTM D2196, and the results of this testing is reported in Table E2 below:

Table E1 B

[00199] As can be seen from the data above, the compositions of the present invention, including Refrigerants 1 - 8 are capable of exhibiting a combination of properties, including viscosity, dielectric constant and boiling point, that provide unexpectedly advantageous performance over the range of temperatures of interest for many of the preferred heat transfer methods of the present invention, including Heat Transfer Method 1 .

Example 2 - Synthesis of TFE/HFP from HFP and TFE

[00200] TFE/HFP is synthesized from HFP and TFE according to the following procedure. 250 mL of DMF and 10 g of cesium carbonate is charged into a 3 necked 500 mL round bottom jacketed flask equipped with a mechanical stirrer, a dry ice condenser, a gas sparger (for HFP) and a temperature sensor. The condenser outlet is attached to a nitrogen tee. Cooling water is turned on before 86 mL of TFE is added. At this point, a slight exotherm is observed. The reaction is allowed to cool to less than 25°C. Next, 200 g of HFP is added over a period of 60 minutes using a sparger and a needle valve such that the temperature of the reaction mixture does not exceed 25°C. The reaction is observed to be exothermic and turns a slight yellow color towards the end of the addition. Once the reaction is almost finished, the exotherm slows and the temperature of the reaction drops quickly. The reaction mixture from the flask is decanted and filtered, then rotovapped at 45°C and 60-70 torr. The reboiler heavies are poured into water and the lower layer (a colorless liquid) is separated to afford 325.0202 g, (801% yield, GC 8385.39%). Alternately, the reaction mixture is decanted, and fully rotovapped under the same conditions to afford 323.8g, (80.6% yield, GC 82.92%). The material is then distilled and combined to give a total of 562.8 g of material over 95% using aby GC with a very sensitive method.

Example 3A - Method and Use of Refrigerant 1 In Fabrication of an Electronic Component

[00201] An electronic component or a portion thereof which is cooled while it undergoes processing during fabrication (such as for example, in the etching of a silicon wafer as illustrated for example in Figure 1 1 ) is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said electronic component) as part of the manufacturing process. Effective temperature control is provided.

Example 3B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of an Electronic Component

[00202] Example 3A is repeated to cool an electronic component while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said electronic component) as part of the manufacturing process. Effective temperature control is provided.

Example 4A - Method and Use of Refrigerant 1 In Fabrication of a Semiconductor Integrated Circuit (IC)

[00203] A semiconductor integrated circuit and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said semiconductor integrated circuit and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 4B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Semiconductor Integrated Circuit (IC)

[00204] Example 4A is repeated to cool a semiconductor integrated circuit while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said semiconductor integrated circuit) as part of the manufacturing process. Effective temperature control is provided.

Example 5A - Method and Use of Refrigerant 1 In Fabrication of an electrochemical cell

[00205] An electrochemical cell and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said electrochemical cell and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 5B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of an electrochemical cell

[00206] Example 5A is repeated to cool a electrochemical cell while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said electrochemical cell) as part of the manufacturing process. Effective temperature control is provided.

Example 6A - Method and Use of Refrigerant 1 In Fabrication of a power transistor

[00207] A power transistors and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said electrochemical cell and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 6B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of an electrochemical cell

[00208] Example 6A is repeated to cool a power transistors while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said power transistor) as part of the manufacturing process. Effective temperature control is provided.

Example 7A - Method and Use of Refrigerant 1 In Fabrication of an Electroluminescent Element [00209] An electroluminescent element and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said electroluminescent element and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 7B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of an electroluminescent element

[00210] Example 7A is repeated to cool an electroluminescent element while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said electroluminescent element) as part of the manufacturing process. Effective temperature control is provided.

Example 8A - Method and Use of Refrigerant 1 In Fabrication of a Microprocessor

[00211] A microprocessor and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said microprocessor and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 8B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Microprocessor

[00212] Example 8A is repeated to cool a microprocessor while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said microprocessor) as part of the manufacturing process. Effective temperature control is provided.

Example 9A - Method and Use of Refrigerant 1 In Fabrication of a Semiconductor Wafer

[00213] A semiconductor wafer and/or a portion thereof which is cooled while it undergoes processing during fabrication (such as for example, in the etching of a silicon wafer as illustrated for example in Figure 1 1 ) is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said semiconductor wafer and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 9B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Semiconductor Wafer

[00214] Example 9A is repeated to cool a semiconductor wafer while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said semiconductor wafer) as part of the manufacturing process. Effective temperature control is provided.

Example 10A - Method and Use of Refrigerant 1 In Fabrication of a Power Control Semiconductor

[00215] A power control semiconductor and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said power control semiconductor and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 10B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Power Control Semiconductor

[00216] Example 10A is repeated to cool a power control semiconductor while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said power control semiconductor) as part of the manufacturing process. Effective temperature control is provided.

Example 11 A - Method and Use of Refrigerant 1 In Fabrication of an Electrical Distribution Switch Gear

[00217] A electrical distribution switch gear and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said electrical distribution switch gear and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 11 B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Power Control Semiconductor [00218] Example 1 1 A is repeated to cool an electrical distribution switch gear while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said electrical distribution switch gear) as part of the manufacturing process. Effective temperature control is provided.

Example 12A - Method and Use of Refrigerant 1 In Fabrication of a Power Transformer

[00219] A power transformer and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said power transformer and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 12B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Power Transformer

[00220] Example 12A is repeated to cool a power transformer while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said electrical distribution switch gear) as part of the manufacturing process. Effective temperature control is provided.

Example 13A - Method and Use of Refrigerant 1 In Fabrication of a Printed Circuit Board (PCB)

[00221] A printed circuit board (PCB) and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said printed circuit board (PCB)and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 13B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Printed Circuit Board (PCB)

[00222] Example 13A is repeated to cool a printed circuit board (PCB)while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said printed circuit boards (PCBs)) as part of the manufacturing process. Effective temperature control is provided.

Example 14A - Method and Use of Refrigerant 1 In Fabrication of a Multi-Chip Module (MCM)

[00223] A MCM and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said MCM and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 14B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a MCM

[00224] Example 14A is repeated to cool a MCM while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said MCM) as part of the manufacturing process. Effective temperature control is provided.

Example 15A - Method and Use of Refrigerant 1 In Fabrication of a Packaged Semi-Conductor Device (PSCD)

[00225] A PSCD and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said PSCD and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 15B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a PSCD

[00226] Example 15A is repeated to cool a PSCD while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said PSCD) as part of the manufacturing process. Effective temperature control is provided.

Example 16A - Method and Use of Refrigerant 1 In Fabrication of a Unackaged Semi-Conductor Device (USCD) [00227] A USCD and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said USCD and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 16B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a USCD

[00228] Example 16A is repeated to cool a USCD while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said USCD) as part of the manufacturing process. Effective temperature control is provided.

Example 18A - Method and Use of Refrigerant 1 In Fabrication of a Fuel Cell

[00229] A fuel cell and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said fuel cell and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 18B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Fuel Cell

[00230] Example 18A is repeated to cool a fuel cell while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said fuel cell) as part of the manufacturing process. Effective temperature control is provided.

Example 19A - Method and Use of Refrigerant 1 In Fabrication of a Laser

[00231] A laser and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said laser and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 19B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of a Laser

[00232] Example 19A is repeated to cool a laser cell while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said laser) as part of the manufacturing process. Effective temperature control is provided.

Example 20A - Method and Use of Refrigerant 1 In Fabrication of a Light Emitting Diode (LED)

[00233] An LED and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said LED and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 20B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of an LED

[00234] Example 20A is repeated to cool a LED while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said LED) as part of the manufacturing process. Effective temperature control is provided.

[00235]

Example 21 A - Method and Use of Refrigerant 1 In Fabrication of an Electrochemical Cell (EC)

[00236] An EC and/or a portion thereof which is cooled while it undergoes processing during fabrication is contacted, directly or indirectly, by Refrigerant 1 to transfer heat between (to and/or from said EC and/or a portion thereof) as part of the manufacturing process. Effective temperature control is provided.

Example 21 B - Method and Use of Refrigerant 2 - Refrigerant 8 and RB1 - RB20 In Fabrication of an EC

[00237] Example 21 A is repeated to cool an EC while undergoing processing, except each of Refrigerant 2 through Refrigerant 8 and each of RB1 through RB2 is used to transfer heat between (to and/or from said EC) as part of the manufacturing process. Effective temperature control is provided.

[00238] It should be understood that the foregoing description is only illustrative of the present disclosure. Various alternatives and modifications can be devised by those skilled in the art without departing from the disclosure. Accordingly, the present disclosure is intended to embrace all such alternatives, modifications and variances that fall within the scope of the appended claims.

Claims

CLAIMS: A method of fabricating an electronic device or component comprising: a. providing at least a portion of an electronic device and/or a component of an electronic device in the process of being fabricated; b. providing a refrigerant comprising 2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)- 1 ,1 ,1 ,3,3,3-hexafluoropropane (HFPOHFP); c. transferring heat, directly and/or indirectly, between said electronic device and/or a component of an electronic device as said device or component is being manufactured. The method of claim 1 wherein said refrigerant is non-flammable. The method of claim 1 wherein said refrigerant comprises at least about 10% by weight of said 2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)-1 ,1 ,1 ,3,3,3-hexafluoropropane. The method of claim 1 wherein said refrigerant comprises at least about 50% by weight of said 2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)-1 ,1 ,1 ,3,3,3-hexafluoropropane. The method of claim 1 wherein said refrigerant comprises at least about 75% by weight of said 2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)-1 ,1 ,1 ,3,3,3-hexafluoropropane. The method of claim 1 wherein said refrigerant comprises at least about 90% by weight of said 2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)-1 ,1 ,1 ,3,3,3-hexafluoropropane. The method of claim 1 wherein said refrigerant consists essentially of said 2- (1 ,1 ,2,3,3,3-hexafluoropropoxy)-1 ,1 ,1 ,3,3,3-hexafluoropropane. The method of claim 1 wherein said refrigerant consists of said 2-(1 ,1 , 2, 3,3,3- hexafluoropropoxy)-1 ,1 ,1 ,3,3,3-hexafluoropropane. The method of claim 1 wherein said refrigerant has a dielectric constant less than about 6 at 20 GHz and a GWP of less than 500. The method of claim 1 wherein the refrigerant has a boiling point of from about 60°C to about 100°C.