composition

Abstract

To provide a nonaqueous electrolytic solution, which provides improved properties over nonaqueous electrolytic solutions of the prior art.SOLUTION: The invention relates to the use of a compound of Formula I in a nonaqueous battery electrolyte formulation, where W is independently selected from the group consisting of H, F, Cl, Br and I; Z is independently selected from the group consisting of H, O(CW2)pCW3, (CW2)pCW3, OCY3, OCW3, polyalkylene glycol and polyolester; n is an integer from 1 to 1000; one of T1 and T2 is W, and the other is (CY2)mCY3; Y is independently selected from the group consisting of F, Cl, Br and I; and p is an integer from 0 to 9.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to non-aqueous electrolytes for energy storage devices, including batteries and capacitors, particularly for secondary batteries and devices known as supercapacitors. [Background technology]

[0002] There are two main types of batteries: primary and secondary. Primary batteries are also known as non-rechargeable batteries. Secondary batteries are also known as rechargeable batteries. A well-known type of rechargeable battery is the lithium-ion battery. Lithium-ion batteries have a high energy density, no memory effect, and low self-discharge.

[0003] Lithium-ion batteries are commonly used in portable electronic devices and electric vehicles. In batteries, lithium ions move from the negative electrode to the positive electrode during discharge and back during charging.

[0004] Typically, the electrolyte contains additives in addition to a non-aqueous solvent and an electrolyte salt. The electrolyte is typically a mixture of organic carbonates such as ethylene carbonate, propylene carbonate, fluoroethylene carbonate, and dialkyl carbonate containing a lithium ion electrolyte salt. Many lithium salts can be used as the electrolyte salt, and common examples include lithium hexafluorophosphate (LiPF), lithium bis(fluorosulfonyl)imide (LiFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

[0005] The electrolyte must perform several distinct roles within the battery.

[0006] The primary role of the electrolyte is to facilitate the flow of charge carriers between the cathode and anode. This occurs by transporting metal ions within the battery to and / or from the anode and / or cathode, where charge is released / gained by chemical reduction or oxidation.

[0007] Therefore, the electrolyte must provide a medium capable of solvating and / or supporting the metal ions.

[0008] Due to the use of lithium electrolyte salts and the exchange of lithium ions with lithium metal, which is highly reactive with water, as well as the sensitivity of other battery components to water, the electrolyte is typically non-aqueous.

[0009] Additionally, the electrolyte must have suitable rheological properties to allow / enhance the flow of ions therein at the typical operating temperatures to which the battery is expected to be exposed and function.

[0010] Additionally, the electrolyte must be as chemically inert as possible. This is particularly relevant in the context of the battery's expected lifespan, with regard to issues of internal corrosion within the battery (e.g., of the electrodes and casing) and battery leakage. Also important to consider in chemical stability is flammability. Unfortunately, typical electrolyte solvents often contain flammable materials, which can be a safety hazard.

[0011] This can be problematic because the battery may accumulate heat during operation while discharging or being discharged. This is especially true for high-density batteries such as lithium-ion batteries. Therefore, it is desirable for the electrolyte to exhibit low flammability along with other related properties such as a high flash point.

[0012] It is also desirable that the electrolyte not pose any environmental issues regarding disposability after use or other environmental issues such as global warming potential. DISCLOSURE OF THE INVENTION

[0013] It is an object of the present invention to provide a non-aqueous electrolyte that offers improved properties over prior art non-aqueous electrolytes.

[0014] The listing or discussion of an apparently prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the state of the art or is common general knowledge.

[0015] Usage According to a first aspect of the present invention, there is provided the use of a compound of formula I in a non-aqueous battery electrolyte formulation.

[0016] According to a second aspect of the present invention, there is provided the use of a non-aqueous battery electrolyte formulation comprising a compound of formula I in a battery.

[0017] Composition / Device Aspects According to a third aspect of the present invention, there is provided a battery electrolyte formulation comprising a compound of formula I.

[0018] According to a fourth aspect of the present invention, there is provided a formulation comprising a metal ion and a compound of formula I, optionally in combination with a solvent.

[0019] According to a fifth aspect of the present invention, a battery is provided that includes a battery electrolyte formulation that includes a compound of formula I.

[0020] Method aspects According to a sixth aspect of the present invention, there is provided a method of reducing the flash point of a battery and / or battery electrolyte formulation comprising the addition of a formulation comprising a compound of formula I.

[0021] According to a seventh aspect of the present invention, there is provided a method of powering an article, comprising using a battery comprising a battery electrolyte formulation comprising a compound of formula I.

[0022] According to an eighth aspect of the present invention, there is provided a method of improving a battery electrolyte formulation, the method comprising either (a) at least partially replacing the battery electrolyte with a battery electrolyte formulation comprising a compound of Formula I, and / or (b) supplementing the battery electrolyte with a battery electrolyte formulation comprising a compound of Formula I.

[0023] According to a ninth aspect of the present invention, there is provided a method of preparing a battery electrolyte formulation comprising mixing a compound of formula I with a lithium-containing salt and other solvents or co-solvents.

[0024] According to a tenth aspect of the present invention, there is provided a method of preparing a battery electrolyte formulation comprising mixing a composition comprising a compound of Formula I with a lithium-containing compound.

[0025] According to an eleventh aspect of the present invention, there is provided a method for improving battery capacity / charge transfer within a battery / battery life / etc. by use of a compound of formula I.

[0026] A compound of formula I, [ka] During the ceremony, W is independently selected from the group consisting of H, F, CI, Br, and I; Y is independently selected from the group consisting of F, CI, Br, and I; Z is H, O(CW2) p CW3, (CW2) p independently selected from the group consisting of CW3OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, One of T1 and T2 is W and the other is (CY2) m It's CY3, A compound wherein p is an integer of 0 to 9.

[0027] Within general formula I, in preferred embodiments, the compound may be one of formula (Ia), (Ib) or (Ic), or a combination thereof. Compounds of formula (Ia) [ka] Compound of formula (Ib) [ka] Compound of formula (Ic) [ka]

[0028] In each case, W is independently selected from the group consisting of H, F, Cl, Br, and I; Y is independently selected from the group consisting of F, Cl, Br, and I; Z is H, O(CW2) p CW3, (CW2) p independently selected from the group consisting of CW3, OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, a and b are each an integer of 1 to 1000, m is an integer from 0 to 3, p is an integer of 0 to 9.

[0029] In compounds of formula (Ic), the subunits of the compound (which mimic the subunits of formula (Ia) and formula (Ib)) can be present in any order in the compound.

[0030] In a preferred embodiment, the compound of formula (Ib) may alternatively be represented by: [ka] In the formula, n is an integer of 1 to 1,000.

[0031] The compounds of formula (I), (Ia), (Ib), (Ic) and (Id) have an M of 100,000 or less, preferably 50,000 or less, and even more preferably 25,000 or less. W may have:

[0032] The compounds of formula (I), (Ia), (Ib), (Ic) and (Id) may have a polydispersity index of about 1.45, preferably about 1.35, more preferably about 1.30, and even more preferably about 1.25.

[0033] In each instance of compounds of formula (I), (Ia), (Ib), (Ic) and (Id): Y is preferably F or Cl, and more preferably Y is F.

[0034] W is preferably H, F or Cl. More preferably, W is H.

[0035] Advantageously, m is an integer between 0 and 3, preferably 0.

[0036] n is preferably an integer of 2 to 1000, for example, an integer of 5 to 500, and preferably an integer of 6 to 100.

[0037] Unless the context dictates otherwise, reference to formula (I) will be understood to include reference to formula (Ia), formula (Ib), formula (Ic) and / or formula (1d).

[0038] In some referenced compounds of Formula (I) (including Formulas (Ia)-(Id)), at least one Z derivative may comprise a polyalkylene glycol. Alternatively, both Z derivatives may comprise a polyalkylene glycol (PAG). In both cases, the polyalkylene glycol may be selected from the group consisting of poly(ethylene) oxide, poly(propylene) oxide, and mixtures thereof. In such embodiments, the PAG group may be conjugated to the compound of Formula (I) through the formation of an ether or ester bond between the hydroxyl end-capping group of Formula (I) (i.e., Z=OH) and an alcohol- or carboxylic acid-end-capped PAG.

[0039] In some compounds of formula (I), at least one Z derivative may comprise a fluorinated PAG (F-PAG). The F-PAG may be selected from the group consisting of an F3C-end-capped PAG and a hydroxyl-end-capped PAG.

[0040] The hydroxyl end groups of F-PAGs can provide further scope for derivatization and can be converted, for example, to ether or ester groups, which can be aliphatic, aromatic, linear, branched, fluorine-containing, or otherwise functionalized to allow further control over product properties.

[0041] In some compounds of formula (I), the Z derivatives may independently be alkyl or alkoxy groups containing from 1 to 10 carbon atoms.

[0042] Both Z derivatives may be the same. Alternatively, both Z derivatives may be different.

[0043] The compound of formula (Ia) may conveniently be a compound of formula (IIa). [ka]

[0044] Those skilled in the art will appreciate that the above formula is merely representative and that structural defects in the polymer chains may exist.

[0045] The composition may, for example, comprise at least two different compounds of formula (I). In such a case, the value of n may be the same for at least two compounds of formula (I). Alternatively, the value of n may be different for at least two compounds of formula (I).

[0046] In some preferred embodiments, the compound of formula (I) is a compound of formula (Ib).

[0047] The compound of formula (I) may be a mixture of compounds of formula (Ia) and (Ib). In this situation, it is preferred that the majority of the mixture is the compound of formula (Ib), for example, more than 50% by weight of the mixture is the compound of formula (Ib), preferably more than 75%, more preferably more than 90% or 95%.

[0048] Compounds of formula (I) may be made by a process involving the polymerization of an epoxide precursor.

[0049] The epoxide precursor has the formula (IV): [ka] During the ceremony, R1 is CF3, R2 is H or F; R3 is H or F; R4 is H or CF3.

[0050] Examples of epoxide precursors that can be used include epoxides according to formula (IV) where R1 is CF3, R2 is H, R3 is H, and R4 is H (epoxide of 3,3,3-trifluoropropene (1243zf)), epoxides according to formula (IV) where R1 is CF3, R2 is F, R3 is H, and R4 is H (epoxide of 2,3,3,3-tetrafluoropropene (1234y ... epoxides according to formula (IV) where R1 is CF3, R2 is H, R3 is F, and R4 is H (epoxide of 1,3,3,3-tetrafluoropropene (1234ze)), and epoxides according to formula (IV) where R1 is CF3, R2 is H, R3 is CF3, and R4 is H (epoxide of 1,1,1,4,4,4-hexafluoro-2-butene (1336mzz)). Preferably, the epoxide is the epoxide of 1243zf (1,1,1-trifluoro-2,3-epoxypropane).

[0051] The method may involve the polymerization of an epoxide using an initiator formed from a base and an alcohol, the selected alcohol being Determine the nature of the Z group in Formulation I.

[0052] Preferably, the base is a Group I or Group II metal hydroxide, more preferably a Group I metal hydroxide, even more preferably sodium hydroxide or potassium hydroxide, even more preferably potassium hydroxide.

[0053] Preferably, the alcohol is a primary alcohol. The primary alcohol is, for example, a C1 to C 10 The primary alcohol may be, for example, a C1-C glycol, preferably ethylene glycol. 10 The primary alcohol may be, for example, a fluorinated alcohol, such as a C1-C 10 The fluorinated alcohol may be of the formula (I), preferably trifluoroethanol.

[0054] The polymerization of the epoxide may be carried out in the absence of a solvent.

[0055] The polymerization reaction can be carried out at a temperature of about 0 to about 130°C, preferably about 40 to about 100°C, and more preferably about 50 to about 90°C.

[0056] The polymerization reaction can be carried out at a pressure of about 100 to about 1000.3 kPa, preferably about 101 kPa.

[0057] It should be noted that the ninth aspect of the invention should be construed as applying to all embodiments of Formula I.

[0058] advantage In embodiments of the present invention, the electrolyte formulation has been found to be surprisingly advantageous.

[0059] The advantages of using compounds of formula I in electrolyte solvent compositions are manifested in several ways. Their presence can reduce the flammability of the electrolyte composition (e.g., as measured by flash point). Their oxidative stability makes them useful in batteries that need to operate under harsh conditions, and they are compatible with common electrode chemistries and can even enhance the performance of these electrodes through their interaction with them.

[0060] Additionally, electrolyte compositions containing compounds of Formula I may have excellent physical properties, including low viscosity and low melting points, but high boiling points with the associated benefit of little or no gassing during use. The electrolyte formulations may wet and spread very well on surfaces, particularly fluorine-containing surfaces, which is hypothesized to result from the beneficial relationship between their adhesive and cohesive strengths to result in low contact angles.

[0061] Additionally, electrolyte compositions containing compounds of Formula I can have superior electrochemical properties. These include improved capacity retention, improved cyclability and capacity, and improved compatibility with other battery components, such as separators and current collectors, and with all types of cathode and anode chemistries (including systems operating over a range of voltages, particularly high voltages, and including systems containing additives such as silicon). Additionally, the electrode formulations exhibit good solvation of metal (e.g., lithium) salts and interaction with any other electrolyte solvents present.

[0062] Preferred features relating to aspects of the present invention are as follows:

[0063] Preferred compounds Preferred compounds of the present invention where n=1 to 50 are shown below. [ka]

[0064] metal salts The non-aqueous electrolyte solution further comprises a metal electrolyte salt present in an amount of 0.1 to 20 weight percent, based on the total weight of the non-aqueous electrolyte formulation.

[0065] Metal salts generally include salts of lithium, sodium, magnesium, calcium, lead, zinc, or nickel.

[0066] Preferably, the metal salt comprises a salt of lithium, such as one selected from the group comprising lithium hexafluorophosphate (LiPF), lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium triflate (LiSOCF), lithium bis(fluorosulfonyl)imide (Li(FSO)N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO)N).

[0067] Most preferably, the metal salt comprises LiPF6. Thus, in a most preferred variant of the fourth aspect of the invention, there is provided a formulation comprising LiPF6 and a compound of formula I, optionally in combination with a solvent.

[0068] Other solvents The non-aqueous electrolyte may contain an additional solvent, preferred examples of which include fluoroethylene carbonate (FEC) and / or propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), or ethylene carbonate (EC).

[0069] When present, the solvent comprises 0.1% to 99.9% by weight of the liquid component of the electrolyte.

[0070] additives The non-aqueous electrolyte may contain additives.

[0071] A suitable additive may serve as a surface film-forming agent that forms an ion-permeable film on the surface of the positive or negative electrode, which can anticipate the decomposition reaction between the non-aqueous electrolyte and the electrolyte salt that occurs on the surface of the electrode, thereby preventing the decomposition reaction of the non-aqueous electrolyte on the surface of the electrode.

[0072] Examples of film-former additives include vinylene carbonate (VC), ethylene sulfite (ES), lithium bis(oxalato)borate (LiBOB), cyclohexylbenzene (CHB), and ortho-terphenyl (OTP). The additives may be used alone or in combination of two or more.

[0073] When present, the additive is present in an amount of 0.1 to 3 weight percent based on the total weight of the non-aqueous electrolyte formulation.

[0074] battery The battery may comprise a primary (non-rechargeable) or secondary (rechargeable) battery. Most preferably, the battery comprises a secondary battery.

[0075] Batteries containing non-aqueous electrolytes will generally contain several elements. The elements that make up a preferred non-aqueous electrolyte secondary battery cell are described below. It is understood that other battery elements may be present (such as a temperature sensor), and the following list of battery components is not intended to be exhaustive.

[0076] electrode Batteries generally contain a positive electrode and a negative electrode. The electrodes are usually porous, allowing metal ions (lithium ions) to enter and exit their structure through a process called intercalation or deintercalation.

[0077] For rechargeable batteries (secondary batteries), the term cathode refers to the electrode where reduction occurs during the discharge cycle. For lithium-ion batteries, the positive electrode ("cathode") is a lithium-based electrode.

[0078] Positive electrode (cathode) The positive electrode is generally composed of a positive electrode current collector, such as a metal foil, and optionally, a positive electrode active material layer disposed on the positive electrode current collector.

[0079] The positive electrode current collector may be a foil of a metal that is stable over the range of potentials applied to the positive electrode, or a film having a skin layer of a metal that is stable over the range of potentials applied to the positive electrode. Aluminum (Al) is a preferred metal that is stable over the range of potentials applied to the positive electrode.

[0080] The positive electrode active material layer generally contains a positive electrode active material and other components such as a conductive agent and a binder. This is generally obtained by mixing the components in a solvent, applying the mixture to the positive electrode current collector, and then drying and rolling.

[0081] The positive electrode active material can be lithium (Li) or a lithium-containing transition metal oxide. The transition metal element can be at least one selected from the group consisting of scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and yttrium (Y). Among these transition metal elements, manganese, cobalt, and nickel are most preferred.

[0082] Furthermore, in certain embodiments, transition metal fluorides may be preferred.

[0083] Some of the transition metal atoms in the transition metal oxide can be replaced by atoms of non-transition metal elements. The non-transition element can be selected from the group consisting of magnesium (Mg), aluminum (Al), lead (Pb), antimony (Sb), and boron (B). Among these non-transition metal elements, magnesium and aluminum are most preferred.

[0084] Preferred examples of the positive electrode active material include lithium-containing transition metal oxides such as LiCoO2, LiNiO2, LiMn2O4, LiMnO2, LiNi 1-y Co y O2 (0 < y < 1), LiNi 1-y-z Co y Mn z O2 (0 < y + z < 1) and LiNi 1-y-z Co y Al z O2 (0 < y + z < 1), etc. LiNi containing nickel at a ratio of 50 mol% or more for all transition metals 1-y-z Co y Mn z O2 (0 < y + z < 0.5) and LiNi 1-y-z Co y Al zO2 (0 < y + z < 0.5) is desirable from the viewpoints of cost and specific capacity. These cathode active materials contain a large amount of alkaline components, and thus accelerate the decomposition of the non-aqueous electrolyte, causing a decrease in durability. However, the non-aqueous electrolyte of the present disclosure is resistant to decomposition even when used in combination with these cathode active materials.

[0085] The cathode active material can be a lithium (Li)-containing transition metal fluoride. The transition metal element can be at least one selected from the group consisting of scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and yttrium (Y). Among these transition metal elements, manganese, cobalt, and nickel are most preferred.

[0086] The conductive agent can be used to increase the electron conductivity of the cathode active material layer. Preferred examples of the conductive agent include conductive carbon materials, metal powders, and organic materials. Specific examples include carbon materials such as acetylene black, ketjen black, and graphite, metal powders such as aluminum powder, and organic materials such as phenylene derivatives. The binder can be used to ensure good contact between the cathode active material and the conductive agent and to increase the adhesion of components such as the cathode active material to the surface of the cathode current collector. Preferred examples of the binder include fluoropolymers and rubber polymers such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-isoprene copolymer, and ethylene-propylene-butadiene copolymer. The binder can be used in combination with a thickener such as carboxymethyl cellulose (CMC) or polyethylene oxide (PEO).

[0087] Negative electrode (anode) The negative electrode is generally composed of a negative electrode current collector such as a metal foil, and optionally, a negative electrode active material layer is disposed on the negative electrode current collector.

[0088] The negative electrode current collector can be a metal foil. Copper (lithium-free) is a suitable metal. Copper is low-cost, easy to process, and has good electronic conductivity.

[0089] Typically, the negative electrode comprises carbon, such as graphite or graphene.

[0090] Silicon-based materials can also be used for the negative electrode. A preferred form of silicon is in the form of nanowires, which are preferably present on a support material. The support material can include metals (such as steel) or non-metals such as carbon.

[0091] The negative electrode may include an active material layer, which, if present, comprises the negative electrode active material and other components, such as a binder, and is generally obtained by mixing the components in a solvent and applying the mixture to a positive electrode current collector, followed by drying and rolling.

[0092] The negative electrode active material is not particularly limited as long as it can store and release lithium ions. Examples of suitable negative electrode active materials include carbon materials, metals, alloys, metal oxides, metal nitrides, and lithium-intercalated carbon and silicon. Examples of carbon materials include natural / artificial graphite and pitch-based carbon fibers. Preferred examples of metals include lithium (Li), silicon (Si), tin (Sn), germanium (Ge), indium (In), gallium (Ga), titanium (Ti), lithium alloys, silicon alloys, and tin alloys. An example of a lithium-based material is lithium titanate (Li2TiO3).

[0093] As with the positive electrode, the binder may be a fluoropolymer or a rubber polymer, preferably a rubbery polymer such as styrene-butadiene copolymer (SBR). The binder may be used in combination with a thickener.

[0094] Separator A separator is preferably present between the positive electrode and the negative electrode. The separator has insulating properties. The separator may include a porous membrane having ion permeability. Examples of porous membranes include microporous thin films, woven fabrics, and nonwoven fabrics. Suitable materials for the separator are polyolefins such as polyethylene and polypropylene.

[0095] case The battery components are preferably disposed within a protective case.

[0096] The case may comprise any suitable resilient material to provide support to the battery and electrical contact to the device being powered.

[0097] In one embodiment, the case comprises a metal material, preferably in sheet form, formed into the shape of the battery. The metal material preferably comprises several parts that are adaptable to be attached together (e.g., by press-fitting) in the assembly of the battery. Preferably, the case comprises an iron / steel-based material.

[0098] In another embodiment, the case comprises a plastic material molded to the battery shape. The plastic material preferably comprises several parts that are adaptable to be joined together (e.g., by press-fitting / adhesion) in the assembly of the battery. Preferably, the case comprises a polymer such as polystyrene, polyethylene, polyvinyl chloride, polyvinylidene chloride, or polymonochlorofluoroethylene. The case may also include other additives for the plastic material, such as fillers or plasticizers. In this embodiment in which the case for the battery primarily comprises a plastic material, a portion of the casing may additionally include a conductive / metallic material for establishing electrical contact with a device powered by the battery.

[0099] arrangement The positive and negative electrodes may be wound or stacked together through a separator. Together with a non-aqueous electrolyte, they are contained within an external case. The positive and negative electrodes are electrically connected to the external case at their separate portions.

[0100] Modules / Packs Several / multiple battery cells may be configured into a battery module, where the battery cells may be organized in series and / or parallel, typically housed in a mechanical structure.

[0101] A battery pack can be assembled by connecting multiple modules together in series or parallel. Typically, the battery pack includes additional features such as sensors and controllers, including battery management systems and thermal management systems. The battery pack generally includes a containment housing structure to form the final battery pack product.

[0102] End use The batteries of the present invention, in the form of individual batteries / cells, modules and / or packs (and electrolyte formulations therefor), are intended to be used in one or more of a variety of end products.

[0103] Preferred examples of end products include portable electronic devices such as GPS navigation devices, cameras, laptops, tablets, and mobile phones. Other preferred examples of end products include vehicular devices (as a supply of electrical power for the propulsion system and / or any other electrical systems or devices present therein) such as electric bicycles and motorcycles, and automotive applications (including hybrid and pure electric vehicles).

[0104] The preferences and options for a given aspect, feature, or parameter of the invention should be considered as disclosed in combination with any and all preferences and options for all other aspects, features, and parameters of the invention, unless the context dictates otherwise.

[0105] The invention will now be described with reference to the following non-limiting examples. [Example]

[0106] The invention is illustrated by the following non-limiting examples.

[0107] The compounds according to the present invention were synthesized by the following method.

[0108] General method The initiator mixture was prepared by adding a certain amount of base (e.g., 85-86% KOH) along with 2-3 drops of Aliquat 336 to alcohol (e.g., ethylene glycol or trifluoroethanol) in a Pyrex round-bottom flask with stirring and cooling. When the base was dissolved in the alcohol, the reaction flask was fitted with a dropping funnel and condenser before adding the epoxide monomer (e.g., 3,3,3-trifluoro-1,2-epoxypropane). The mixture was then heated with stirring. At the end of the reaction, the product was cooled and dissolved in a minimum amount of chloroform (e.g., 250 ml). This chloroform solution was washed with acidic water (e.g., 4 g of 36% HCl in 100 ml of water) and then washed three times with water alone (e.g., 100 ml). The washed chloroform solution of the polymer product was dried over anhydrous sodium sulfate, filtered, and the solvent removed by distillation under reduced pressure.

[0109] The resulting polymer products were analyzed and characterized by gel permeation chromatography (GPC).

[0110] GPC was performed on a Shimadzu Prominence LC system equipped with an RI detector having a 300 mm × 75 mm, 5 μm PLgel 100 A and a 300 mm × 7.5 mm, 5 μm PLgel 500 A column in series with a THF eluent at 1.0 ml / min at 40°C. The method was calibrated with poly(styrene) standards with MWs ranging from 1000 to 10000.

[0111] Viscosity Measurements: Viscosity measurements were performed on a TA Instruments Discovery Hybrid Rheometer at 10 rad / s from -20 to 70°C using a 40 mm 2.008° cone-plate geometry.

[0112] Using this general method, a series of polymer products were produced, and the details of each preparation and key properties of each product are outlined in Table 1. [Table 1]

[0113] The preparative procedure used in Example 2 was scaled up to give 1440 g of F(F) product, which was dissolved in tetrahydrofuran (THF, 1000 ml) and cooled to 5° C. Potassium t-butoxide (220 g) was added portionwise to the THF solution so that the temperature did not exceed 10° C.

[0114] The resulting solution was stirred for 30 minutes, after which methyl iodide (142 g) was added. The reaction mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was then quenched with water (2000 ml), and after phase separation, the organic layer was washed five more times with water (1000 ml). The organic layer was dried over anhydrous MgSO4, after which the THF solvent and other volatiles were removed by vacuum distillation at 90°C and 1 mmHg for 1-2 hours. The final product was treated with activated carbon and filtered to remove haze, yielding 1100 g of the product of Formula I. [ka] [Table 2]

[0115] composition Compositions containing the products of Formula I (as in the preparative examples above) were prepared as shown in Table 2 below. [Table 3]

[0116] Flammability and Safety Tests flash point Flash points were determined according to the ASTM D6450 standard method using a Miniflash FLP / H device from Grabner Instruments. [Table 4]

[0117] These measurements indicate that the addition of an additive called F-PAGF(F) methyl end cap increased the flash point of the standard electrolyte.

[0118] Self-extinguishing time The self-extinguishing time was measured with a custom-made device that included an automatically controlled stopwatch connected to an ultraviolet detector. The electrolyte to be tested (500 μL) was applied to a Whatman GF / D (Φ=24 mm) glass microfiber filter. An ignition source was moved under the sample and held in this position for a preset time (1, 5, or 10 seconds) to ignite the sample. Ignition and combustion of the sample was detected using a UV photodetector. The evaluation is based on the burn time / weight of electrolyte [sg -1 ] over the ignition time [s] and extrapolating with a linear regression line to ignition time = 0 s. ·Self-extinguishing time (sg -1 ) is the time required for the sample to stop burning once ignited. [Table 5]

[0119] Electrochemical Testing Drying Prior to testing, the F-PAGF(F) methyl end-caps were dried by treatment with pre-activated type 4A molecular sieves. The water levels of the pre- and post-treated samples were determined by the Karl Fischer method. [Table 6]

[0120] electrolyte formulation Electrolyte preparation and storage were carried out in an argon-filled glove box (HO and O < 0.1 ppm). The base electrolyte was 1 M LiPF in ethylene carbonate:ethyl methyl carbonate (3:7 wt%) with concentrations of F-PAGF(F) methyl end-capping additive of 2, 5, 10, and 30 wt%.

[0121] Cell Chemistry and Structure The performance of each electrolyte formulation was tested in multi-layer pouch cells (2 cells per electrolyte) for 50 cycles. Chemistry 1: Lithium-nickel-cobalt-manganese-oxide (NCM622) cathode and artificial graphite (specific capacity: 350 mAh g -1 ) anode. The areal capacities of NMC622 and graphite are 3.5 mAh cm, respectively. -2 and 4.0mAh cm -2 The N / P ratio reached 115%. Chemistry 2: Lithium-nickel-cobalt-manganese-oxide (NCM622) cathode and SiO x / Graphite (specific capacity: 550mAh g -1 ) Negative electrode: NMC622 and SiO x / graphite areal capacity is 3.5mAh / cm -2 and 4.0mAh cm -2 The N / P ratio reached 115%. The test pouch cell had the following characteristics: ·Nominal capacity 240mAh + / -2% Standard deviation: Capacity: ±0.6mAh Coulombic efficiency (CE) 1st cycle: ±0.13% Coulombic efficiency (CE) subsequent cycles: ±0.1% Positive electrode: NMC-622 ·Active material content: 96.4% ·Mass load: 16.7mg cm -2 Negative electrode: Artificial graphite ·Active material content: 94.8% ·Mass load: 10mg cm -2 Separator: PE (16 μm) + 4 μm Al2O3 Balanced at 4.2V cutoff voltage Negative electrode: Artificial graphite + SiO ·Active material content: 94.6% ·Mass load: 6.28mg cm -2 Separator: PE (16 μm) + 4 μm Al2O3 Balanced at 4.2V cutoff voltage After assembly, the following fabrication protocol was used. 1. Step charge to 1.5V followed by a 5-hour rest step (wet step at 40°C) 2. CCCV(C / 10, 3.7V(I 限界 : 1 hour) (pre-formation step) 3. Rest step (6 hours) 4. CCCV(C / 10, 4.2V(I 限界 :0.05C)) Rest step (20 min) 5. CC discharge (C / 10, 3.8V), (cell degassing) 6.CC discharge (C / 10, 2.8V) Following this formation step, the cells were tested as follows. Rest step (1.5V, 5 hours), CCCV (C / 10, 3.7V (1 hour)) Rest step (6 hours), CCCV(C / 10, 4.2V(I 限界 :0.05C)) Rest step (20 min), CC discharge (C / 10, 3.8 V) Degassing step Discharge (C / 10, 2.8V), rest step (5 hours) CCCV(C / 3, 4.2V(I 限界 :0.05C), rest step (20 min) ·CC discharge (C / 3, 2.8V) 50 cycles or until 50% SOH is reached at 40°C: CCCV(C / 3, 4.2V(I 限界 :0.02C), rest step (20 min) CC discharge (C / 3, 3.0V), rest step (20 min)

[0122] Test results The test results for the additive F-PAGF(F) methyl end-cap in each cell chemistry are summarized in Tables 3 and 4 and Figures 3 and 4. From this data, it can be confirmed that the additive in both cell chemistries had a positive impact on cell performance. These results, combined with safety-related studies, demonstrate that the compounds of the present invention simultaneously improved both the safety and performance of energy storage devices containing them. [Table 7] [Table 8] [Brief explanation of the drawings]

[0123] [Figure 1] 1 shows the 19F NMR spectra of compositions A1, A2 and A3. [Figure 2] 1 shows the 19F NMR spectra of compositions B1 and B2. [Figure 3] Figure 1 shows the electrochemical performance of F-PAGF(F) methyl end-capped cell chemistry 1. [Figure 4] Figure 1 shows the electrochemical performance of F-PAGF(F) methyl end-capped cell chemistry 2.

[0124] The present invention includes the following aspects. [Aspect 1] 1. Use of a compound of formula I in a non-aqueous battery electrolyte formulation, comprising: [ka] During the ceremony, W is independently selected from the group consisting of H, F, CI, Br, and I; Y is independently selected from the group consisting of F, CI, Br, and I; Z is H, O(CW2) p CW3, (CW2) p independently selected from the group consisting of CW3OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, One of T1 and T2 is W and the other is (CY2) m It's CY3, Use where p is an integer from 0 to 9. [Aspect 2] 10. The use according to embodiment 1 of a compound of Formula (Ia), (Ib), or (Ic) in a non-aqueous battery electrolyte formulation, comprising: [ka] During the ceremony, W is independently selected from the group consisting of H, F, Cl, Br, and I; Y is independently selected from the group consisting of F, Cl, Br, and I; Z is H, O(CW2) p CW3, (CW2) p CW3, OCY3, OCW3, polyalkylene glycol, and polyol ester, n is an integer of 1 to 1000, and m is a is an integer of 0 to 3, p is an integer of 0 to 9, and a and b are each an integer of 1 to 1000. [Aspect 3] 1. Use of a non-aqueous battery electrolyte formulation comprising a compound of formula I, (Ia), (Ib) or (Ic) in a battery. [Aspect 4] 4. The use of any one of the preceding aspects, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 wt. %, based on the total mass of the non-aqueous electrolyte formulation. [Aspect 5] 5. The use according to aspect 4, wherein the metal salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc or nickel. [Aspect 6] 6. The use of embodiment 5, wherein the metal salt is a salt of lithium selected from the group consisting of lithium hexafluorophosphate (LiPF), lithium hexafluoroarsenate monohydrate (LiAsF), lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium triflate (LiSOCF), lithium bis(fluorosulfonyl)imide (Li(FSO)N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO)N). [Aspect 7] Use according to any one of aspects 1 to 6, wherein the formulation comprises an additional solvent in an amount of 0.1% to 99.9% by weight of the liquid components of the formulation. [Aspect 8] 8. The use according to embodiment 7, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC) or ethylene carbonate. [Aspect 9] A battery electrolyte formulation comprising a compound of formula I, (Ia), (Ib) or (Ic). [Aspect 10] 1. A formulation comprising a metal ion and a compound of formula I, optionally in combination with a solvent, [ka] During the ceremony, W is independently selected from the group consisting of H, F, CI, Br, and I; Y is independently selected from the group consisting of F, CI, Br, and I; Z is H, O(CW2) p CW3, (CW2) pindependently selected from the group consisting of CW3, OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, One of T1 and T2 is W and the other is (CY2) m It's CY3, The formulation wherein p is an integer from 0 to 9. [Aspect 11] 1. A battery comprising a battery electrolyte formulation comprising a compound of formula I, [ka] During the ceremony, W is independently selected from the group consisting of H, F, CI, Br, and I; Y is independently selected from the group consisting of F, CI, Br, and I; Z is H, O(CW2) p CW3, (CW2) p independently selected from the group consisting of CW3, OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, One of T1 and T2 is W and the other is (CY2) m It's CY3, A battery, wherein p is an integer from 0 to 9. [Aspect 12] 12. The formulation of any one of aspects 9-11, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 wt. %, based on the total weight of the non-aqueous electrolyte formulation. [Aspect 13] Aspect 13. The formulation of aspect 12, wherein the metal salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc, or nickel. [Aspect 14] 14. The formulation of embodiment 13, wherein the metal salt is a salt of a lithium salt selected from the group consisting of lithium hexafluorophosphate (LiPF), lithium hexafluoroarsenate monohydrate (LiAsF), lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium triflate (LiSOCF), lithium bis(fluorosulfonyl)imide (Li(FSO)N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO)N). [Aspect 15] 15. The formulation of any one of aspects 9-14, wherein the formulation comprises an additional solvent in an amount between 0.1% and 99.9% by weight of the liquid components of the formulation. [Aspect 16] 16. The formulation of embodiment 15, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC), and ethylene carbonate (EC). [Aspect 17] 1. A method of reducing the flammability of a battery and / or battery electrolyte comprising the addition of a formulation comprising a compound of formula I, [ka] During the ceremony, W is independently selected from the group consisting of H, F, CI, Br, and I; Y is independently selected from the group consisting of F, CI, Br, and I; Z is H, O(CW2) p CW3, (CW2) p independently selected from the group consisting of CW3, OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, One of T1 and T2 is W and the other is (CY2) m It's CY3, The method wherein p is an integer from 0 to 9. [Aspect 18] 1. A method of powering an article comprising using a battery comprising a battery electrolyte formulation comprising a compound of formula I, [ka] During the ceremony, W is independently selected from the group consisting of H, F, CI, Br, and I; Y is independently selected from the group consisting of F, CI, Br, and I; Z is H, O(CW2) p CW3, (CW2) p independently selected from the group consisting of CW3, OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, One of T1 and T2 is W and the other is (CY2) m It's CY3, The method wherein p is an integer from 0 to 9. [Aspect 19] 1. A method of improving a battery electrolyte formulation, comprising either (a) at least partially replacing the battery electrolyte with a battery electrolyte formulation comprising a compound of Formula I, and / or (b) supplementing the battery electrolyte with a battery electrolyte formulation comprising a compound of Formula I; [ka] During the ceremony, W is independently selected from the group consisting of H, F, CI, Br, and I; Y is independently selected from the group consisting of F, CI, Br, and I; Z is H, O(CW2) p CW3, (CW2) p independently selected from the group consisting of CW3, OCY3, OCW3, polyalkylene glycols and polyol esters; n is an integer from 1 to 1000, One of T1 and T2 is W and the other is (CY2) m It's CY3, The method wherein p is an integer from 0 to 9. [Aspect 20] 1. A process for preparing a formulation containing a compound of formula I by polymerization of an epoxide precursor of formula (IV), comprising the steps of: [ka] During the ceremony, The method wherein R1 is CF3, R2 is H or F, R3 is H or F, and R4 is H or CF3. [Aspect 21] A method of preparing a battery electrolyte formulation comprising mixing an electrolyte with a compound of formula I. [Aspect 22] A method for improving battery capacity / charge transfer within a battery / battery life / etc. by using compounds of formula I. [Aspect 23] 23. The method of any one of aspects 17-22, wherein the formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 wt. %, based on the total weight of the non-aqueous electrolyte formulation. [Aspect 24] 24. The method of embodiment 23, wherein the metal salt is a lithium, sodium, magnesium, calcium, lead, zinc, or nickel salt. [Aspect 25] 25. The method of claim 24, wherein the metal salt is a salt of lithium selected from the group comprising lithium hexafluorophosphate (LiPF), lithium hexafluoroarsenate monohydrate (LiAsF), lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium triflate (LiSOCF), lithium bis(fluorosulfonyl)imide (Li(FSO)N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CFSO)N). [Aspect 26] 26. The method of any one of aspects 17-25, wherein the formulation comprises an additional solvent in an amount between 0.1% and 99.9% by weight of the liquid components of the formulation. [Aspect 27] 27. The method of embodiment 26, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC), and ethylene carbonate (EC).

Claims

1. Epoxide precursor of formula (IV): 【Chemical 1】 wherein R 1 is CF 3 , R 2 is H or F, R 3 is H or F, and R 4 is H or CF 3 , to give a compound of formula I: 【Chemistry 2】 (In the formula, W is independently selected from the group consisting of H, F, Cl, Br, and I; Y is independently selected from the group consisting of F, Cl, Br, and I; Z is independently selected from the group consisting of H, O(CW2)pCW3, (CW2)pCW3, OCY3, OCW3, polyalkylene glycols, and polyol esters; n is an integer from 1 to 1000, one of T 1 and T 2 is W and the other is (CY 2 ) m CY 3 ; m is an integer from 0 to 3; and p is an integer from 0 to 9.

2. i) R 1 is CF 3 , R 2 is H, R 3 is H, and R 4 is H, or ii) R 1 is CF 3 , R 2 is F, R 3 is H and R 4 is H; or iii) R 1 is CF 3 , R 2 is H, R 3 is F and R 4 is H; or iv) The method of claim 1, wherein R 1 is CF 3 , R 2 is H, R 3 is CF 3 , and R 4 is H.

3. A method according to claim 1 or 2, wherein the method comprises polymerizing an epoxide using an initiator formed from a base and an alcohol, the alcohol selected determining the nature of the Z group in formula I.

4. The method of claim 3, wherein the base is a Group I or Group II metal hydroxide, more preferably a Group I metal hydroxide, even more preferably sodium hydroxide or potassium hydroxide, even more preferably potassium hydroxide.

5. The method described in claim 3 or 4, wherein the alcohol is a primary alcohol.

6. The method of claim 1, wherein the polymerization of the epoxide is carried out in the absence of a solvent.

7. The method of claim 1, wherein the polymerization is carried out at a temperature of about 0 to about 130°C.

8. The method of claim 1, wherein the polymerization is carried out at a pressure of about 100 to about 1000.3 kPa.

9. The method of claim 1, wherein after polymerization, the electrolyte is mixed with the compound of formula I to form a non-aqueous battery electrolyte formulation.

10. 10. The method of claim 9, wherein the non-aqueous battery electrolyte formulation comprises a metal electrolyte salt present in an amount of 0.1 to 20 weight percent, based on the total weight of the non-aqueous battery electrolyte formulation.

11. 11. The method of claim 10, wherein the metal electrolyte salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc, or nickel.

12. The metal electrolyte salt is lithium hexafluorophosphate (LiPF ６ ), lithium hexafluoroarsenate monohydrate (LiAsF ６ ), lithium perchlorate (LiClO ４ ), lithium tetrafluoroborate (LiBF ４ ), lithium triflate (LiSO ３ CF3), lithium bis(fluorosulfonyl)imide (Li(FSO ２ ) ２ N) and lithium bis(trifluoromethanesulfonyl)imide (Li(CF ３ SO ２ ) ２ 12. The method of claim 11, wherein the lithium salt is selected from the group consisting of:

13. 13. The method of any one of claims 9 to 12, wherein the non-aqueous battery electrolyte formulation comprises an additional solvent in an amount of 0.1% to 99.9% by weight of the liquid component of the non-aqueous battery electrolyte formulation.

14. 14. The method of claim 13, wherein the additional solvent is selected from the group comprising fluoroethylene carbonate (FEC), propylene carbonate (PC) and ethylene carbonate (EC).

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